JP5646572B2 - Modified fiber and method for producing the same - Google Patents

Description

  The present invention relates to a modified fiber and a method for producing the same. More specifically, the present invention relates to a modified fiber in which an epoxy compound is bonded to purified cellulose fiber, natural cellulose fiber, copper ammonia rayon, rayon or silk fiber, and a method for producing the same.

  Silk fibers are known for their unique luster and good touch, and are widely used as high-grade fibers. Purified cellulose fiber and copper ammonia rayon are regenerated cellulose fibers that imitate silk fibers, and have a gloss and feel similar to silk fibers. Examples of such regenerated cellulose fibers include “Tencel (registered trademark)” and “Lyocell (registered trademark)”, which are purified cellulose fibers sold by Lenzing, and copper ammonia sold by Asahi Kasei Fibers, Inc. A typical example is “Bemberg (registered trademark)” which is a rayon.

  Silk and regenerated cellulose fibers have high utility value for clothing, but on the other hand, they have low chemical resistance, wrinkle resistance, dimensional stability, friction resistance, etc. It is known that fibrillation of fibers occurs due to friction, and the texture is deteriorated or a whitening phenomenon (hereinafter also referred to as white blurring) occurs.

  For this reason, various attempts have been made in the past to improve the above characteristics. For example, Japanese Examined Patent Publication No. 47-024199 (Patent Document 1) discloses a method of obtaining fibers having high chemical resistance by treating fibers in one bath in which a neutral salt catalyst and an epoxy compound coexist. Proposed. Hideki Shiozaki, “Present and Future of Washable Silk”, Processing Technology, 1989, Vol. 24, no. 2, pages 74-77 (Non-Patent Document 1) proposes a method of obtaining processed silk with less fluff by heat-treating silk in an aqueous solution containing an ethylene glycol epoxy compound.

Japanese Examined Patent Publication No. 47-024199

Hideki Shiozaki, “Present and Future of Washable Silk”, Processing Technology, 1989, Vol. 24, no. 2, pages 74-77

  However, in the said nonpatent literature 1, a specific epoxy compound is unknown, and the friction resistance of the silk fiber produced in the said patent document 1 is also unknown. And the technology which improves the friction resistance of refined cellulose fiber, copper ammonia rayon, and silk fiber is not yet sufficient, and it is the actual condition that development of the further technology is advanced.

  The present invention has been made in view of the above-described situation, and an object of the present invention is to provide a modified fiber having high wear resistance when wet and high washing resistance and a method for producing the same. The purpose is to provide.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies, and can impart high friction resistance to silk fibers by crosslinking an epoxy compound having two epoxy groups in silk fibroin. And based on this idea, the present inventors have also studied cellulose fibers and rayon and completed the present invention.

  That is, the modified fiber of the present invention is a refined cellulose fiber, a natural cellulose fiber, copper ammonia rayon or a modified fiber in which an epoxy compound is bound to rayon, and the epoxy compound contains resorcinol diglycidyl ether and hydroquinone diglycidyl ether. It is characterized by being at least one of these.

  Further, a modified fiber in which an epoxy compound is bonded to silk fiber, and the epoxy compound has at least one of resorcinol diglycidyl ether and hydroquinone diglycidyl ether, and has the same effect as the present invention. .

Here, the modified fiber preferably further contains a quaternary ammonium salt.
The present invention also relates to a method for producing the modified fiber, which comprises immersing purified cellulose fiber, natural cellulose fiber, copper ammonia rayon or rayon in a treatment liquid containing an epoxy compound, A step of bonding the epoxy compound to purified cellulose fiber, natural cellulose fiber, copper ammonia rayon or rayon, wherein the epoxy compound is at least one of resorcinol diglycidyl ether and hydroquinone diglycidyl ether It is a manufacturing method of a modified fiber.

  In addition, the method includes a step of immersing silk fiber in a treatment liquid containing an epoxy compound and bonding the epoxy compound to the silk fiber, wherein the epoxy compound is at least one of resorcinol diglycidyl ether and hydroquinone diglycidyl ether The method for producing a modified fiber, which is characterized in that, has the same effect as the present invention.

  Here, the treatment liquid preferably contains a quaternary ammonium salt.

  The modified fiber of the present invention is a fiber having high wear resistance, and exhibits excellent wear resistance particularly when wet. In addition, the modified fiber of the present invention has a very small dimensional change between drying and wetting, and can have high washing resistance. Furthermore, according to the manufacturing method of this invention, the modified fiber which has said characteristic can be manufactured.

  In the present specification, the high friction resistance is an index indicating the difficulty of occurrence of fiber fluff and white blurring. Silk fibers tend to be fibrillated (small fibers) due to rubbing and interfacial fibers, resulting in fluffing and white blurring. As a result, the friction resistance of silk fibers tends to be low. By improving the friction property, it becomes difficult to cause fuzz and white blurring.

  The bath ratio is an index indicating the ratio of the treatment liquid (ml) to the fiber weight (g). For example, when 5 g of silk fiber is treated in 100 ml of treatment liquid, the bath ratio is 1:20, and when 5 g of silk fiber is treated in 200 ml of treatment liquid, the bath ratio is 1:40. . That is, the 1:20 bath ratio is less in the amount of the treatment liquid relative to the silk fiber weight than the 1:40 bath ratio, and the 1:20 bath ratio is lower than the 1:40 bath ratio. It will be.

  For example, when the substance A is 5 g and the substance B is 0.5 g, the weight ratio of the substance B to the substance A is calculated by the weight of the substance B / the weight of the substance A × 100. The value is 10%.

It is a figure which shows the surface state after the friction test of the silk crepe produced in Experimental example 1. FIG. It is a figure which shows the surface state after the washing test of the silk crepe produced in Experimental example 1. FIG. It is a figure which shows the surface state after the friction test of the silk crepe produced in Experimental example 2. FIG. It is a figure which shows the surface state after the washing test of the silk crepe produced in Experimental example 2. FIG. It is a figure which shows the surface state after the friction test of the silk crepe produced in the comparative experiment example 1. FIG. It is a figure which shows the surface state after the washing test of the silk crepe produced in the comparative experiment example 1. FIG. It is a figure which shows the surface state after a friction test of the silk feather double 6cm produced in Experimental example 3. FIG. It is a figure which shows the surface state after the friction test of the double silk feathers produced in Experimental Example 4. It is a figure which shows the surface state after the friction test of the silk feather double 6cm produced in the comparative experiment example 2. FIG. It is a figure which shows the surface state after the friction test of the knitted fabric using the silk spun yarn produced in Experimental example 13. FIG. It is a figure which shows the surface state after the washing test based on 103 method of the knitted fabric using the silk spun yarn produced in Experimental example 13. FIG. It is a figure which shows the surface state after the friction test of the knitted fabric using the silk spun yarn produced in the comparative experiment example 7. FIG. It is a figure which shows the surface state after the washing test based on 103 method of the knitted fabric using the silk spun yarn produced in the comparative experiment example 7. FIG. It is a figure which shows the state of the short fiber after the fibril resistance test of the processed refined cellulose fiber produced in Example 1. FIG. It is a figure which shows the state of the short fiber after the fibril resistance test of the processed refined cellulose fiber produced in Example 2. FIG. It is a figure which shows the state of the short fiber after the fibril resistance test of the purified cellulose fiber of the comparative example 1. It is a figure which shows the state of the short fiber after the fibril resistance test of the processed refinement | purification cellulose fiber produced in the comparative example 2. FIG. It is a figure which shows the state of the short fiber after the fibril resistance test of the processed refinement | purification cellulose fiber produced in the comparative example 3. FIG. It is a figure which shows the state of the short fiber after the fibril resistance test of the processed copper ammonia rayon produced in Example 3. FIG. It is a figure which shows the state of the short fiber after the fibril resistance test of the copper ammonia rayon of the comparative example 4. It is a figure which shows the state of the short fiber after the fibril resistance test of the processed silk fiber produced in Reference Example 1. FIG. It is a figure which shows the state of the short fiber after the fibril resistance test of the silk fiber of the comparative reference example 1. FIG.

Hereinafter, the modified fiber of the present invention will be described in detail.
<Modified fiber>
The modified fiber of the present invention is a modified fiber in which an epoxy compound is bonded to purified cellulose fiber, natural cellulose fiber, copper ammonia rayon or rayon. Further, the modified fiber in which an epoxy compound is bonded to silk fiber also exhibits excellent characteristics like the modified fiber of the present invention.

≪Purified cellulose fiber≫
The purified cellulose fiber used as the base material of the modified fiber of the present invention is a kind of regenerated cellulose fiber, which is obtained by dissolving wood pulp or the like in an organic solvent, filtering through a filter, removing impurities, and spinning. Fiber. Typical examples include “Tencel (registered trademark)” and “Lyocell (registered trademark)”. Purified cellulose fiber is superior in strength because it does not undergo derivatization by chemical decomposition of raw material cellulose. Further, natural cellulose may be used instead of purified cellulose as the base material of the modified fiber of the present invention. Examples of natural cellulose fibers include cotton and hemp.

≪Copper ammonia rayon≫
Copper ammonia rayon, which is a base material for the modified fiber of the present invention, is a kind of regenerated fiber. After removing cotton collected from a cotton linter in a copper ammonia solution (Schweitzer solution) and filtering it through a filter, impurities It is a fiber obtained by removing and spinning. A representative example is “Bemberg (registered trademark)”. Moreover, rayon can also be used for the base material of the modified fiber of the present invention.

≪Silk fiber≫
Silk fiber can also be used as the base material of the modified fiber. Silk fibers include silk fabric, silk knitted fabric, silk yarn, silk spun yarn, silk short fiber, and the like. In addition to plain weave and twill weave, silk fabric includes not only fiber structures such as crimps having a three-dimensional structure by twisting.

  Here, the refined cellulose fiber, natural cellulose fiber, copper ammonia rayon and rayon also include woven fabrics, knitted fabrics, long fiber yarns, spun yarns, short fibers, etc. In addition, fiber structures such as crimps having a three-dimensional structure by twisting are included.

≪Epoxy compound≫
The epoxy compound includes at least resorcinol diglycidyl ether (hereinafter also referred to as “RDGE”) represented by the following chemical formula (1) and hydroquinone diglycidyl ether (hereinafter also referred to as “HDGE”) represented by the following chemical formula (2). Either one. That is, in the modified silk fiber, either RDGE or HDGE may be bonded, or both may be bonded.

  The modified fiber of the present invention can have high friction resistance. Further, if the weight ratio of the epoxy compound to the fiber is 0.7% or more, it can have a sufficiently high friction resistance, and more preferably 1.8% or more. In addition, even if the weight ratio of the epoxy compound to the fiber is 5% or less, it can have a sufficiently high friction resistance, thereby suppressing a decrease in texture caused by bonding an excessive epoxy compound to the fiber. Can do.

  In the modified fiber of the present invention, although the above-mentioned polymerization ratio of RDGE and / or HDGE is significantly lower than the polymerization ratio of other epoxy compounds, for example, the epoxy compound described in Patent Document 1, to the fibers, The details of the reason for having high friction resistance are not clear, but the present inventors presume the reason as follows.

  That is, when the fiber to be modified is silk fiber, RDGE and HDGE have two epoxy groups in one molecule, and therefore can be crosslinked in silk fibroin. Therefore, even if the polymerization ratio is low, that is, even when the amount of the epoxy compound bonded to the modified fiber is small, the structure of the silk fibroin can be sufficiently strengthened, and as a result, high friction resistance can be imparted. . Moreover, since RDGE and HDGE have a phenyl group in the molecule, they can bind more to the tyrosine group having a chemically similar structure in silk fibroin, and as a result, the structure of silk fibroin can be efficiently formed. Can be stabilized.

  In addition, when the fibers to be modified are refined cellulose fibers, natural cellulose fibers, copper ammonia rayon and rayon, two epoxy compounds possessed by RDGE and HDGE are based on functional groups such as hydroxyl groups in the molecule. It is considered that it is crosslinked by a group. By cross-linking, the fibrils inside the fiber are bound together, and fine grooves existing between the fibrils are filled. As a result, when friction is applied, the starting point at which the fiber tears and separates into a plurality of fibrils decreases, and as a result, wear resistance can be improved.

≪Quaternary ammonium salt≫
The modified fiber of the present invention can further improve the wear resistance by having a quaternary ammonium salt. Here, examples of the quaternary ammonium salt include a quaternary ammonium salt having a chlorohydrin group, a quaternary ammonium salt having an epoxy group, a quaternary ammonium salt having a triazine group, polyallylamine, and polyethyleneimine. it can. For example, 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2,3-epoxypropylmethylammonium chloride, monochloroethyldiethylamine, glycidyltrimethylammonium chloride and the like can be used. Further, it may be a polyquaternary ammonium salt. Of these, 3-chloro-2-hydroxypropyltrimethylammonium chloride and 2,3-glycidyltrimethylammonium chloride are preferred.

  The present inventors have found that when the modified fiber of the present invention contains a quaternary ammonium salt together with the above epoxy compound, higher abrasion resistance can be expressed. Although the details of the mechanism by which such an effect is obtained are unknown, the presence of the quaternary ammonium salt promotes crosslinking by the epoxy compound, and increases the hydrogen bond and intermolecular force between the fibrils. It is presumed that the binding is further strengthened and the fibers are hardly divided into fibrils.

Hereinafter, the production method of the present invention will be described in detail.
<Method for producing modified fiber>
The production method of the present invention includes a step of immersing the fiber in a treatment liquid containing at least one of RDGE and HDGE epoxy compounds to bond the epoxy compound to the fibers.

  It is preferable to use water as the treatment liquid because of its low production cost and ease of handling. The treatment liquid contains the above-described epoxy compound, but the epoxy compound is dispersed in a dispersant such as an organic solvent or an emulsifier so that the epoxy compound is more uniformly dispersed in the treatment liquid. A treatment liquid may be prepared. In this case, for example, a treatment liquid can be prepared by gradually adding water to a mixture of an emulsifier and an epoxy compound and dispersing the emulsifier and the epoxy compound in water.

  For the dispersant, it is preferable to use a material that does not inhibit the binding reaction of the epoxy compound to the silk fibers. For example, emulsifiers such as Disper VG (manufactured by Meisei Chemical Co., Ltd.), Saisol 2EX (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), BK57NM (manufactured by Nikka Chemical Industry Co., Ltd.) can be used. An organic solvent such as dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) can be used. In addition, in the process liquid, the other substance which is not intended may be mixed in the range which does not inhibit the binding reaction of the epoxy compound to the fiber.

  The amount of the epoxy compound added in the treatment liquid is not particularly limited, but the present inventors set the concentration of the epoxy compound during the treatment to 3% owf (immersing the weight of the epoxy compound contained in the treatment liquid in the treatment liquid). It has been found that modified fibers having high friction resistance can be produced with high yield even at a low concentration (percentage of value divided by the weight of the fiber structure).

  Therefore, it is preferable to prepare a treatment liquid containing an epoxy compound having a weight of 3% or more based on the weight of the fiber immersed in the treatment liquid. Thereby, a modified fiber can be manufactured efficiently, and also the manufacturing cost can be reduced by being able to restrict | limit the usage-amount of an epoxy compound appropriately.

  Moreover, it is preferable that the treatment liquid further contains a quaternary ammonium salt. The addition amount of the quaternary ammonium salt in the treatment liquid is preferably 1 g / l or more and 15 g / l or less. By including the quaternary ammonium salt in this range, crosslinking by the epoxy compound is promoted, so that the amount of the epoxy compound used can be reduced and the wear resistance can be further enhanced by a synergistic effect. If the addition amount is less than 1 g / l, the above effect tends to be difficult to obtain, and it is not preferable. If it exceeds 15 g / l, the finished modified fiber has a high dyeing speed and causes problems such as uneven dyeing. Absent. Here, the method of including the quaternary ammonium salt in the treatment liquid is not particularly limited. For example, the treatment liquid may be directly added to the treatment liquid containing the epoxy compound and the dispersant, or may be previously added to a solvent such as water. After the dispersion, the dispersion may be added to the treatment liquid and stirred.

  As described above, any of woven fabric, knitted fabric, long fiber yarn, spun yarn, and short fiber may be used as the fiber immersed in the treatment liquid. For example, when a modified fiber is produced by immersing a woven fabric or a knitted fabric in the treatment liquid, various products such as clothing can be efficiently produced using the modified fiber such as a woven fabric or a knitted fabric. For example, when a modified fiber is produced by immersing long fiber yarn, spun yarn, short fiber, etc., a woven fabric and a knitted fabric can be produced using the modified fiber. The present inventors have found that the woven fabric and the knitted fabric thus produced not only have high friction resistance, but also have a property that they are difficult to shrink.

  Moreover, the bath ratio of the fiber immersed in a process liquid is not restrict | limited in particular, For example, it can be set to 1: 5 or more. In particular, when the fiber immersed in the treatment liquid is a knitted fabric or a woven fabric, the fiber bath ratio is preferably 1:15 or more and 1:30 or more in order to avoid manufacturing troubles during the treatment. More preferably, the ratio is more preferably 1:50 or more. As a result, the knitted fabric or the fabric and the treatment tank can be prevented from rubbing in the treatment liquid, and the knitted fabric or the fabric itself can be prevented from rubbing, so that the modified fiber can be produced while suppressing the occurrence of fuzz and white blurring. it can. However, from the viewpoint of production efficiency, production cost, and the speed of the bonding reaction of the epoxy compound, the bath ratio should be set regardless of whether fibers of woven fabric, knitted fabric, long fiber yarn, spun yarn, or short fiber are used. It is preferable to set it low.

  Moreover, in the said process, it is preferable to heat a process liquid, adding the catalyst for promoting the coupling | bonding of the epoxy compound to a fiber to the process liquid in which the fiber was immersed. Thereby, the rate of the bonding reaction of the epoxy compound can be further increased, and the epoxy compound can be bonded to the fiber with high bonding efficiency.

  As the catalyst, for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, tin tetrachloride, boron trifluoride, amine, thiocyanate and the like can be used. Especially, it is preferable to use alkaline catalysts, such as sodium hydroxide and sodium hydrogencarbonate, at the point which has the high catalytic ability with respect to RDGE and HDGE. The concentration of the catalyst in the treatment liquid is not particularly limited and can be appropriately adjusted. For example, the catalyst preferably contains 5 to 10 times the concentration (mol) of the epoxy compound in the treatment liquid, more preferably contains 6 to 9 times the catalyst, and more preferably 8 times the catalyst. It is more preferable to contain.

  The heating method is not particularly limited, and for example, a heating method in which the temperature of the processing solution at room temperature (25 ° C.) is gradually raised to 50 ° C. to 80 ° C. may be used. A heating method that maintains the temperature may be used. The heating time is not particularly limited, and can be, for example, 30 minutes or more and 180 minutes or less.

  According to the said manufacturing method, at least one of RDGE and HDGE can be combined with the silk fibroin which comprises a silk fiber. The modified silk fiber bonded with RDGE and / or HDGE has high friction resistance, and has excellent properties such that fuzzing and white blurring hardly occur. That is, according to the said manufacturing method, the modified silk fiber which has high friction resistance can be manufactured.

  Further, according to the above production method, the modified cellulose fiber, natural cellulose fiber, copper ammonia rayon or rayon is cross-linked with an epoxy compound so that the modified fiber having high friction resistance can be obtained in the same manner as the silk fiber. Can be manufactured. Further, when the above treatment liquid further contains a quaternary ammonium salt, the friction resistance can be further improved.

  As described above, according to the above manufacturing method, since the treatment can be performed even at a high bath ratio, it is possible to effectively prevent the fibers from being slid during the process. Generation of blur can be suppressed. Further, as described above, since the bonding efficiency of RDGE and HDGE to the fiber is high, it is possible to efficiently bond the epoxy compound with a small amount of the epoxy compound used, and as a result, the manufacturing cost can be reduced. .

  Hereinafter, examples of the present invention will be described, but these examples are for better understanding of the present invention and do not limit the scope of the present invention.

[Experiment (1) Production and Evaluation of Modified Silk Wrinkles]
First, a modified silk crepe was produced and its friction resistance was evaluated.

(Experimental example 1)
First, 0.25 g of RDGE (Denacol EX201; manufactured by Nagase ChemteX Corporation) and 0.5 g of a dispersant (Disper VG; manufactured by Meisei Chemical Co., Ltd.) were well kneaded, and this kneaded material was stored in a stirring tank. And the processing liquid containing RDGE was prepared by adding water gradually to a kneaded material and making it emulsify-disperse. The total amount of water used was 200 ml. Next, 5 g of silk crepe (manufactured by Nagahama Chirimen Co., Ltd.) was immersed in the prepared treatment solution. The basis weight of the silk crepe was 150 g / m ² . In order to make the bonding of the epoxy compound to the silk crepe uniform, the treatment liquid in which the silk crepe was immersed was stirred.

  Then, while gradually adding a diluted sodium hydroxide aqueous solution obtained by diluting 1.25 g of a 24% sodium hydroxide aqueous solution with 50 ml of water to the stirred processing liquid, the temperature of the processing liquid is increased from 25 ° C. to 60 ° C. Allowed to warm. Thereafter, the treatment liquid was continuously stirred for 60 minutes while maintaining the temperature of the treatment liquid at 60 ° C.

By the above-mentioned treatment, silk crepe with RDGE bonded thereto was produced. The silk crepe is washed with water, washed with 2 g / l sodium dithionite aqueous solution (Na ₂ S ₂ O ₄ ), washed with warm water, washed with water, and then dried. A processed silk crepe was prepared. Two processed silk creases were produced.

(Experimental example 2)
First, a solution obtained by dissolving 0.25 g of HDGE (Denacol EX203; manufactured by Nagase ChemteX Corporation) in 0.7 g of DMF and 1.7 g of a dispersant (Disper VG; manufactured by Meisei Chemical Co., Ltd.) are often used. The kneaded mixture was stored in a stirring tank. And the process liquid was prepared by the method similar to Experimental example 1. Except for the above, a processed silk crepe was produced in the same manner as in Experimental Example 1. Two processed silk creases were produced.

(Comparative Experimental Example 1)
Silk crease was treated in the same manner as in Experimental Example 1 except that RDGE and a dispersant were not used. That is, in Comparative Experimental Example 1, as in Experimental Examples 1 and 2, the silk crepe was subjected to immersion treatment, washing treatment, etc., but the epoxy compound was not bonded to the silk crepe. Two processed silk creases were produced.

(Blue dyeing process)
In the friction test described later, the treated silk creases produced in Experimental Examples 1 and 2 and Comparative Experimental Example 1 were dyed in blue one by one so that the occurrence of white blur could be easily observed. Specifically, dyeing treatment was performed by immersing the treated silk koji in dyeing solution A having the following composition and stirring at 60 ° C. for 60 minutes. Each treated silk koji after dyeing was immersed in a cleaning solution containing 3 g / l of a nonionic active agent (ECB-50; manufactured by Dainichi Seika Kogyo Co., Ltd.) and washed with stirring at 60 ° C. for 30 minutes. And each processed silk crepe after stirring washing was washed in order of washing with warm water and washing with water, and then dried.

[Stain A]
Sumifix Brill Blue R (manufactured by Sumika Chemtex Co., Ltd.): 7% owf
Newbon MRW (Nikka Chemical Co., Ltd.): 1% owf
Anhydrous sodium sulfate: 40 g / l
Sodium carbonate: 4 g / l
(Black dyeing process)
In the washing test described later, the processed silk creases produced in Experimental Examples 1 and 2 and Comparative Experimental Example 1 were dyed black one by one so that the occurrence of white blurring was easily observed. Specifically, the dyed silk was processed by immersing the processed silk koji in the dyeing solution B having the following composition and stirring at 70 ° C. for 60 minutes. Each processed silk crepe after dyeing was immersed in a cleaning solution containing 5 g / l of a nonionic active agent (ECB-50; manufactured by Dainichi Seika Kogyo Co., Ltd.) and washed by stirring at 60 ° C. for 30 minutes. And each processed silk crepe after stirring washing was washed in order of washing with warm water and washing with water, and then dried.

[Staining solution B]
Funder Riactive Black BG (manufactured by Sumika Chemtex Co., Ltd.): 15% owf
Newbon MRW (Nikka Chemical Co., Ltd.): 1% owf
Anhydrous sodium sulfate: 50 g / l
Sodium carbonate: 20 g / l
(Friction experiment)
Using a Gakushin type friction fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), a friction test was performed on each processed silk crepe dyed in blue. Specifically, 100 reciprocating friction cloths were slid with respect to the processed silk crimps while applying a load of 100 g using a friction cloth made of cotton cloth containing water in the same amount as the weight of the cloth. After the friction test, fluffing and white blurring on the friction surface of the treated silk crepe were confirmed by magnifying and observing 200 times with a microscope.

(Laundry test)
Using a home electric washing machine (manufactured by Toshiba Appliances Co., Ltd.), according to JIS L 0217 103 method, a washing test was performed on each processed silk crepe dyed in black. Specifically, first, treated silk crimped rice was introduced into an electric washing machine for home use, and a cloth made of polyester was introduced as a load cloth. Next, water at 45 ° C. was added to an electric washing machine for home use so that the bath ratio of the processed silk crepe was 1:50, and a 3 g / l polyoxyethylene alkyl ether-based neutral detergent (Acron) ; Lion Co., Ltd.) was put in, and the washing test was conducted for 50 minutes, and then laid flat and dried. After the washing test, fluffing and white blurring on the surface of the treated silk crepe were confirmed by magnifying and observing 200 times with a microscope.

(result)
FIG. 1 shows the surface state after the friction test and FIG. 2 shows the surface state after the washing test for the treated silk crepe produced in Experimental Example 1. Moreover, about the processed silk crepe produced in Experimental example 2, the surface state after a friction test is shown in FIG. 3, and the surface state after a washing test is shown in FIG. FIG. 5 shows the surface state after the friction test and FIG. 6 shows the surface state after the washing test for the treated silk crepe produced in Comparative Experimental Example 1. In addition, each figure image | photographed the image | video which expanded the surface of each processed silk crepe 200 times using the microscope.

  When FIGS. 1 and 2 are compared with FIGS. 5 and 6, fuzz and white blur are not observed in FIGS. 1 and 2, whereas fuzz and white blur are observed in FIGS. 5 and 6. From this result, it was found that the friction resistance of silk crease was improved by binding RDGE to silk crepe. Similarly, neither fuzz nor white blur was observed in FIGS. From this result, it was found that the friction resistance of silk crease was improved by bonding HDGE to silk crepe as an epoxy compound.

[Experiment (2) Production and Evaluation of Modified Silk Feather Double 6cm]
(Experimental example 3)
The same method as in Experimental Example 1 except that 5 g of silk double cocoon (manufactured by Hadano Machine Industry (Fukushima)) was used instead of 5 g of silk crepe (manufactured by Nagahama Chirimen Co., Ltd.) Thus, a treated silk feather double 6cm was prepared. The basis weight of the double silk feathers was 20 g / m ² .

(Experimental example 4)
A treated silk double double cocoon was produced in the same manner as in Experimental Example 2 except that 5 g of the above silk double double cocoon was used instead of 5 g silk crepe (manufactured by Nagahama Chirimen Co., Ltd.). .

(Comparative Experiment Example 2)
A treated silk double double cocoon was prepared in the same manner as in Comparative Experiment 1 except that 5 g of the above silk double double cocoon was used instead of 5 g silk crepe (manufactured by Nagahama Chirimen Co., Ltd.). did.

(Blue dyeing treatment and friction test)
The treated silk feather double 6 cocoons produced in Experimental Examples 3 and 4 and Comparative Experimental Example 2 were dyed blue by the same blue dyeing method as described above, and then subjected to the same friction test as described above. .

(result)
FIG. 7 shows the surface state after the friction test of the treated silk wing double 6 mm produced in Experimental Example 3. FIG. 8 shows the surface state after the friction test of the treated silk wing double 6 mm produced in Experimental Example 4. FIG. 9 shows the surface state after the friction test of the treated silk wing double 6 mm produced in Comparative Experimental Example 2. In addition, each figure is the image | video which expanded and imaged the surface of each processed silk feather double 6 squares 200 times.

  7 and 8 are compared with FIG. 9, fuzz and white blur are not observed in FIGS. 7 and 8, whereas fuzz and white blur are observed in FIG. 9. From this result, it was found that the rub resistance of the silk wing double 6 向上 was improved by bonding RDGE to the silk wing double 6 匁.

[Experiment (3) Examination of epoxy compounds]
According to the above experiments (1) and (2), the friction resistance of the silk fiber structure can be improved by bonding RDGE and HDGE to a silk fiber structure such as silk cocoon and double silk wings. all right. Therefore, the above-mentioned effects of RDGE and HDGE were compared with the case where other epoxy compounds were bonded.

(Experimental example 5)
Except that 0.4 g of RDGE (Denacol EX201; manufactured by Nagase ChemteX Corporation) and 0.5 g of a dispersant (Disper VG; manufactured by Meisei Chemical Co., Ltd.) were well kneaded in the same manner as in Experimental Example 1. A processed silk crepe was prepared.

(Experimental example 6)
A treated silk crease was prepared in the same manner as in Experimental Example 2, except that 0.4 g of HDGE (Denacol EX203; manufactured by Nagase ChemteX Corporation) was dissolved in 0.7 g of DMF.

(Comparative Experiment 3)
A treated silk crepe was prepared in the same manner as in Experimental Example 1 except that 0.4 g of diethylene glycol diglycidyl ether (Epolite 100E; manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of RDGE.

(Comparative Experimental Example 4)
A treated silk crepe was prepared in the same manner as in Experimental Example 1 except that 0.4 g of glycerol polyglycidyl ether (Denacol EX313; manufactured by Nagase ChemteX Corporation) was used instead of RDGE. The glycerol polyglycidyl ether is a mixture of glycerol diglycidyl ether and glycerol triglycidyl ether.

(Comparative Experimental Example 5)
A treated silk crease was prepared in the same manner as in Experimental Example 1 except that 0.4 g of 1,6-hexanediol diglycidyl ether (Denacol EX212; manufactured by Nagase ChemteX Corporation) was used instead of RDGE. did.

(Comparative Experimental Example 6)
A treated silk crepe was prepared in the same manner as in Experimental Example 1 except that 0.4 g of hydrogenated bisphenol A diglycidyl ether (Epolite 4000; manufactured by Kyoeisha Yushi Chemical Co., Ltd.) was used instead of RDGE.

(Blue dyeing treatment and friction test)
The treated silk creases produced in Experimental Examples 5 and 6 and Comparative Experimental Examples 3 to 6 are dyed blue by the same blue dyeing method as described above, and then subjected to the same friction test as described above. Was used to observe the rubbed surface of the treated silk crepe.

(result)
Fluffing and white blurring were not observed on the surface after the friction test of the treated silk creases produced in Experimental Example 5 and Experimental Example 6. On the other hand, fuzz and white blur were observed on the surface after the friction test of the treated silk creases produced in Comparative Experimental Examples 3-6. From this result, it was found that silk crepe to which RDGE and HDGE were bonded had higher friction resistance than silk fibers to which a conventional epoxy compound was bonded.

  Moreover, although the epoxy compound used in Comparative Experimental Examples 3 to 6 is an epoxy compound that is considered to have an effect of modifying silk fibers in Patent Document 1 and Non-Patent Document 1, this study In addition, fuzz and white blur were observed after the friction test. As one of the reasons, for example, the following can be considered.

  That is, in the present study, the ratio of the silk crepe bath in the treatment liquid is as high as 1:40 to 1:50, the concentration of the epoxy compound in the treatment liquid is as low as 8% owf, and the concentration relative to the solution is 2 g / 1 and low. In the case of such treatment conditions, the epoxy compound used in Comparative Experimental Examples 3 to 6 cannot be sufficiently bonded to the silk fibroin of the silk crepe, and as a result, the produced modified silk crease has friction resistance. Cannot have sex.

[Experiment (4) Examination of addition amount of epoxy compound]
From the result of the experiment (3), it was found that the bonding efficiency of the RDGE or HDGE epoxy compound to the silk fiber is high. The bonding efficiency of the epoxy compound is a percentage of a value obtained by dividing the weight of the epoxy compound bonded to the modified silk fiber by the weight of the epoxy compound contained in the treatment liquid before immersing the silk fiber. . It was also found that RDGE and HDGE bonded to silk fibers have higher friction resistance than when other epoxy compounds are bonded. Therefore, the following examination was performed.

  Specifically, by using the respective treatment liquids in which the weights of RDGE contained in the treatment liquid were 0.15 g, 0.25 g, and 0.35 g, respectively, by the same method as in Experimental Example 1, the processed silk crepe (Experimental Examples 7 to 9). In addition, each treatment liquid having a weight of RDGE of 0.5 g, 0.6 g, and 0.7 g was used, and a diluted sodium hydroxide aqueous solution in which 5 g of a 24% sodium hydroxide aqueous solution was diluted with 50 ml of water was used. By the same method as Experimental example 1, the processed silk crepe was produced (Experimental examples 10-12).

  And the weight of each processed silk crepe was measured and the weight increase rate of each processed silk crease was computed. In addition, also when the processed silk crepe was produced by the method similar to Experimental Example 1 without adding RDGE, the weight of the treated silk crease slightly decreased. This is due to the fact that the scouring of the silk crepe was not complete and the residual sericin in each silk crease was removed by the above treatment. Therefore, each weight increase rate was calculated after blank-correcting the weight change rate of the processed silk crepe treated with the treatment liquid not containing RDGE as 0%.

  The results are shown in Table 1. In Table 1, the weight (g) of RDGE contained in the prepared treatment liquid, the concentration (% owf) of RDGE contained in the prepared treatment liquid with respect to silk wrinkle, and the weight increase rate (% ) And RDGE binding efficiency (%) are shown in order from the left. In addition, the weight increase rate of the silk crepe is obtained by blank-correcting a percentage obtained by dividing the weight of the silk crease after the treatment by the weight of the silk crease used in the treatment.

  Moreover, as reference experiment examples 1-5, the weight increase rate (%) of the silk fiber calculated based on the result of Examples 1-5 described in patent document 1, and the binding efficiency (%) of an epoxy compound are shown. It is shown in 2.

  Referring to Table 1, it was found that even when the concentration of RDGE in the treatment solution was as low as 3% owf, RDGE bound to silk crepe with a high binding efficiency of 26%. It was also found that the efficiency of RDGE binding to silk folds was further improved by setting the concentration of RDGE in the treatment liquid to 5% owf or higher. On the other hand, referring to Table 2, in spite of being treated with the epoxy compound at a high concentration of 160% owf, the binding efficiency of the epoxy compound to the treated silk fiber may be less than 10%. Understood. From this, it was found that by modifying silk fiber using RDGE and HDGE, it becomes possible to efficiently use the epoxy compound, thereby improving the production efficiency and reducing the production cost. .

  In addition, referring to Table 1, silk crepe treated with RDGE as an epoxy compound has high friction resistance even at a relatively low weight increase rate of 5% or less, while Table 2 shows Referring to silk fibers treated with other epoxy compounds, the friction resistance was low despite a relatively high weight gain rate of 8.3% or more. From this, it is understood that by using RDGE as the epoxy compound, high friction resistance can be imparted with a smaller amount of bonding than when other epoxy compounds are used. Therefore, it was found that the modified silk fiber to which RDGE was bonded can suppress a decrease in the texture of the silk fiber due to excessive bonding of the epoxy compound.

  Further, it was found that even when the amount of the catalyst (sodium hydroxide) relative to the treatment liquid is as small as 5 g / l and 20 g / l, RDGE binds to silk crepe with high binding efficiency. Therefore, manufacturing cost can be reduced by using RDGE as an epoxy compound. In addition, the low amount of catalyst used reduces the amount of catalyst that is incorporated and / or adhered to the produced modified silk fiber. Accordingly, it is possible to suppress a decrease in the texture of the silk fiber due to the catalyst adhering to the silk fiber.

[Experiment (5) Production and evaluation of modified silk spun yarn]
In the said experiment (1)-(4), it examined using the silk fabric. On the other hand, in Experiment (5), examination was performed using silk spun yarn. The silk spun yarn is a spun silk short fiber.

(Experimental example 13)
First, 25 g of RDGE (Denacol EX201; manufactured by Nagase ChemteX Corporation) and 50 g of a dispersant (Disper VG; manufactured by Meisei Chemical Co., Ltd.) are well kneaded, and water is gradually added to the kneaded material to emulsify and disperse. Thus, a treatment liquid containing RDGE was prepared. The total amount of water used was 500 ml. Next, 500 g of silk spun yarn (SPCC; manufactured by Shenyang Silk Spinning Co., Ltd.) with count MC2 / 60 was wound around a dyeing tube and set in a cheese dyeing machine. Next, the above treatment liquid was gradually added while circulating 4000 ml of water through the cheese dyeing machine.

  And the temperature of the process liquid was raised from 25 degreeC to 60 degreeC, adding the dilute sodium hydroxide aqueous solution which diluted 25 g of 24% sodium hydroxide aqueous solution with 500 ml of water gradually to a cheese dyeing machine. Thereafter, the treatment liquid was further circulated for 60 minutes while maintaining the temperature of the treatment liquid at 60 ° C.

By the above treatment, silk spun yarn to which RDGE was bonded was produced. The silk spun yarn was washed with water, washed with 2 g / l sodium dithionite aqueous solution (Na ₂ S ₂ O ₄ ), washed with warm water, washed with water, and then dried. Thus, a processed silk spun yarn was produced.

(Comparative Experimental Example 7)
Treated silk spun yarn by the same method as in Experimental Example 13 except that the amount of water circulated in the cheese dyeing machine and the amount of the 24% aqueous sodium hydroxide solution used were changed without using RDGE and a dispersant. Was made. Specifically, in Comparative Experimental Example 7, 5 g of 24% sodium hydroxide was gradually added directly to the cheese dyeing machine while 5000 ml of water was circulated through the cheese dyeing machine.

(Black dyeing treatment, friction test and washing test)
Next, a black dyeing process was performed on the processed silk spun yarn produced in Experimental Example 13 and Comparative Experimental Example 7 using a cheese dyeing machine. In addition, the said dyeing | staining liquid B was used for the black dyeing | staining process. After the dyeing treatment, a knitted fabric having a width of 10 cm and a length of 30 cm was produced using a cylindrical knitting machine (number of needles: 180; manufactured by Maruzen Sangyo Co., Ltd.). Thereafter, the same friction test as described above was performed, and the surface of the knitted fabric was observed using a microscope. Further, according to JIS L 0217 103 method, each knitted fabric was washed 30 times by the same method as described above, and the surface of each knitted fabric after washing was observed using a microscope.

(result)
About the knitted fabric using the processed silk spun yarn produced in Experimental Example 13, the surface state after the friction test and the surface state after the washing test are shown in FIGS. 10 and 11, respectively. About the knitted fabric using the processed silk spun yarn produced in the comparative experiment example 7, the surface state after a friction test and the surface state after a washing test are shown in FIG. 12 and FIG. 13, respectively. Each figure is an image obtained by enlarging the surface of the knitted fabric using each processed spun silk yarn by 200 times.

  When comparing FIGS. 10 and 11 with FIGS. 12 and 13, fuzz and white blur were not observed in FIGS. 10 and 11, whereas fuzz and white blur were observed in FIGS. From this result, it was found that when RDGE was bonded to a silk spun yarn and a knitted fabric was produced using this, the friction resistance of the knitted fabric was improved.

  In addition, with respect to each knitted fabric produced in Experimental Example 13 and Comparative Experimental Example 7, treated silk was applied while applying a load of 100 g using a friction cloth made of cotton cloth containing water equal to the cloth weight. The surface of the knitted fabric after the 200 reciprocating friction cloth was slid against the crimp was observed. Also in this case, as in the case of 100 reciprocating slides, fuzz and white blur were not observed in the knitted fabric produced in Experimental Example 13, whereas the knitted fabric produced in Comparative Experimental Example 7 was observed. In addition, fuzz and white blur were observed.

(Dimensional stability test (1))
Next, a knitted fabric was prepared according to the following creation conditions using the treated spun yarn produced in Experimental Example 13 and the treated spun yarn after the black dyeing treatment.
Knitting machine: 14-gauge flat knitting machine (Shimae Seisakusho Co., Ltd.)
Knitting organization: Tendon knitted fabric Size: 25cm x 50cm (length x width)
And according to JIS L 0217 103 method, the knitted fabric was washed 10 times and the change of the dimension of the knitted fabric after washing was measured. The dimensional change is marked by sewing white thread on both ends of the knitted fabric 40cm wide in the longitudinal direction and 20cm width in the lateral direction before washing, and the length between the positions of the marks after washing. Observed by measuring. Table 3 shows the dimensions of the knitted fabric before and after washing.

  Referring to Table 3, the knitted fabric of Experimental Example 13 was found to be stable with no significant change in its dimensions before and after the washing treatment. Therefore, it was found that by producing a knitted fabric using the processed spun yarn, a product having high friction resistance and high dimensional stability can be provided using the knitted fabric.

[Experiment (6) Production and Evaluation of Modified Cellulose Fiber and Modified Rayon]
Fibers modified by the production method of the present invention were produced using purified cellulose fibers and copper ammonia rayon, and fibril resistance and dimensional stability were evaluated.

Example 1
First, “Tencel (registered trademark)” (titer: 1.4 dtex, fiber length: 38 mm) sold by Lenzing Co. was prepared as purified cellulose fiber.

  Next, 5 g (5.0 owf%) of RDGE (Denacol EX201; manufactured by Nagase ChemteX Corporation) and 5 g (5.0 owf%) of a dispersant (Disper VG; manufactured by Meisei Chemical Co., Ltd.) The kneaded material was stored in a stirring tank of a liquid circulation type dyeing machine (Obermeier dyeing machine). And the processing liquid containing RDGE was prepared by adding water gradually to a kneaded material and making it emulsify-disperse. The total amount of water used was 1000 ml. Further, the treatment liquid contains 10 g (10 g / l) of a quaternary ammonium salt (Cathionone KCN; 4-chloro-2-hydroxypropyltrimethylammonium chloride and 2,3-glycidyltrimethylammonium chloride as the main components. A grade ammonium salt (manufactured by Yushi Kogyo Co., Ltd.) was added and stirred, and uniformly dispersed. Next, 100 g of purified cellulose fiber was immersed in the treatment liquid.

  Then, 8 g (8 g / l) of 24% aqueous sodium hydroxide solution diluted with 50 ml of water was added in 3 portions to the stirred processing solution, and the temperature of the processing solution was 25 ° C. To 80 ° C. Thereafter, the treatment liquid was continuously stirred for 45 minutes while maintaining the temperature of the treatment liquid at 80 ° C.

By the above treatment, purified cellulose fibers to which RDGE was bonded were produced. The fibers were washed with water and then washed with 4 g / l sodium dithionite aqueous solution (Na ₂ S ₂ O ₄ ) at 60 ° C. for 10 minutes. Furthermore, after washing at 60 ° C. for 10 minutes using a 2 g / l aqueous acetic acid solution, washing with water was finally performed, followed by dehydration and drying to produce treated purified cellulose fibers.

(Example 2)
A treated purified cellulose fiber was produced in the same manner as in Example 1 except that the quaternary ammonium salt (Cathionone KCN) was not added to the treatment liquid in Example 1.

(Comparative Example 1)
As Comparative Example 1, “Tencel (registered trademark)” (titer: 1.4 dtex, fiber length: 38 mm) sold by Lenzing was used without treatment.

(Comparative Example 2)
In Example 1, treated refined cellulose fibers were produced in the same manner as in Example 1 except that RDGE (Denacol EX201) and a dispersant (Disper VG) were not added to the treatment liquid.

(Comparative Example 3)
A treated purified cellulose fiber was produced in the same manner as in Comparative Example 2, except that the amount of quaternary ammonium salt (Cathionone KCN) added to the treatment solution was 50 g / L.

Example 3
As a copper ammonia rayon, “Bemberg (registered trademark)” (Titer: 1.4 dtex, fiber length: 38 mm) sold by Asahi Kasei Fibers Co., Ltd. was prepared. A treated copper ammonia rayon was produced in the same manner as in Example 1 except that.

(Comparative Example 4)
As Comparative Example 4, “Bemberg (registered trademark)” (Titer: 1.4 dtex, fiber length: 38 mm) sold by Asahi Kasei Fibers Corporation was used without treatment.

(Reference Example 1)
As a silk fiber, silk sliver A1 (Makiki; manufactured by Zhejiang Tongxiang Heshan Boshoku Boshoku Co., Ltd.) was prepared, and in Example 1, except that the purified cellulose fiber was used as a silk fiber, the same as in Example 1. A treated silk fiber was prepared.

(Comparative Reference Example 1)
As a comparative reference example 1, silk sliver A1 (Masaki, Zhejiang Tongxiang Heshan Weiwei Textile Co., Ltd.) was used without any treatment.

(Fiber resistance test)
In order to evaluate the fibril resistance of the fibers of Examples 1 and 2 and Reference Example 1 and Comparative Examples 1 to 4 and Comparative Reference Example 1 produced as described above, the following tests were performed.

  First, the fiber of Example 1 was cut to obtain a plurality of short fibers having a length of 3.0 mm or less. Next, 3.3 g of a plurality of short fibers were weighed, and 500 ml of water was put into a household mixer (Pure Black TM series; manufactured by Tescom Co., Ltd.). Next, the mixture was stirred for 2 minutes with a home mixer and then left for 10 minutes. The same stirring and leaving operations were repeated, and a total of 12 operations were performed.

  Next, after adding 500 ml of water in the mixer, the short fibers and water in the mixer were transferred to a plastic container. Next, the pouring spout of the plastic container was completely covered and fixed with a nylon mesh sheet (mesh width 80 μm), and then the plastic container was inverted, and the amount of water flowing out from the inside in 50 seconds was measured. .

  Here, the amount of water flowing out in 50 seconds can be used as an index of the fibril resistance of the short fibers stirred by the mixer. When fibrillation occurs due to friction under wet conditions, the generated fibrils do not pass through the mesh and become clogged, so that the amount of water flowing out within a certain time decreases. Therefore, in the above test, it shows that the greater the amount of water flowing out, the better the fibril resistance.

  The above test was similarly performed for Example 2 and Reference Example 1, and Comparative Examples 1 to 4 and Comparative Reference Example 1. The results are shown in Table 4.

  As is apparent from Table 4, the modified fibers of the examples obtained by the production method of the present invention have superior fibril resistance as compared with the comparative examples.

  From the results of Comparative Examples 1 to 3, the fibril resistance of the purified cellulose fiber is improved by increasing the addition amount of the quaternary ammonium salt, but the fibril resistance of Example 1 bonded to the epoxy compound is improved. Is not enough. Moreover, it can be seen from the results of Examples 1 and 2 that the fibril resistance of the purified cellulose fiber is further improved by using a quaternary ammonium salt together with the epoxy compound. In Comparative Example 3, although the fibril resistance is improved, the dyeability is greatly deteriorated and the practicality is poor.

  Similarly, from the results of Example 2 and Comparative Example 4 and the results of Reference Example 1 and Comparative Reference Example 1, copper ammonia rayon and silk fiber were also modified by the production method of the present invention, thereby improving fibril resistance. It turns out that it improves notably.

  Moreover, the image which dried the short fiber after said fibril resistance test and expanded and magnified 800 times with the microscope is shown in FIGS. 14-22.

  As apparent from FIGS. 14 to 22, the modified fibers of the examples generate very little fibrils (small fibers). On the other hand, in the fiber of the comparative example, generation of fibrils is observed. Further, it is understood from the comparison between FIG. 14 and FIG. 15 that generation of fibrils can be further suppressed by using a quaternary ammonium salt together with an epoxy compound.

(Dimensional stability test (2))
Next, in order to evaluate the dimensional stability of the fibers of Examples 1 and 2 and Reference Example 1, and Comparative Examples 1 and 4 and Comparative Reference Example 1, the following tests were performed.

  First, in accordance with JIS L 1013: 2010 “Chemical Fiber Staple Test Method” (8.7.1 “Standard Time Test”), the elongation percentage Sd (%) during drying of the fiber of Example 1 was measured. The measurement environment was 20 ° C. and relative humidity 60%.

  Next, in accordance with JIS L 1013: 2010 “Chemical Fiber Staple Test Method” (8.7.2 “Wet Test”), the elongation percentage Sh (%) of the fiber of Example 1 when wet was measured. The water temperature during the measurement was 20 ° C.

  Then, ΔS was calculated by the following formula: ΔS (%) = Sh (%) − Sd (%). Here, ΔS is an index of dimensional stability (that is, washing resistance) when repeated washing is performed. The smaller ΔS, the smaller the change in elongation between dry and wet, indicating that the dimensions are more stable even after repeated washing and drying.

  The above test was similarly performed for Example 3 and Reference Example 1, and Comparative Examples 1 and 4 and Comparative Reference Example 1. The results are shown in Table 5.

  As is clear from Table 5, the fiber of the example to which the epoxy compound is bonded has an extremely small ΔS and excellent dimensional stability as compared with the fiber of the comparative example. That is, it has high washing resistance.

  As described above, the modified fiber of the present invention is a modified fiber in which an epoxy compound is bonded to purified cellulose fiber or copper ammonia rayon, and the epoxy compound is at least one of resorcinol diglycidyl ether and hydroquinone diglycidyl ether. Therefore, it was confirmed that the modified fiber had both high wear resistance and washing resistance. Further, it was confirmed that the abrasion resistance and the washing resistance were further improved by binding the quaternary ammonium salt to the modified fiber. This fact indicates that the same effect can be obtained even if the base material of the modified fiber is natural cellulose fiber or rayon.

  Although the embodiments and examples of the present invention have been described above, it is also planned from the beginning to appropriately combine the features of the embodiments and examples.

  The embodiments and examples disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the embodiments and examples described above but by the scope of claims for patent, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims for patent.

  The present invention can be widely used to improve the abrasion resistance and washing resistance of textile products.

Claims (4)

A modified fiber in which an epoxy compound is bonded to purified cellulose fiber, natural cellulose fiber, copper ammonia rayon or rayon,
The epoxy compound, Ri least either one der resorcinol diglycidyl ether and hydroquinone diglycidyl ether,
A modified fiber, wherein a weight ratio of the epoxy compound to the modified fiber is 0.7% or more and 5% or less .   The modified fiber according to claim 1, further comprising a quaternary ammonium salt. A manufacturing method for manufacturing the modified fiber according to claim 1,
A step of immersing purified cellulose fiber, natural cellulose fiber, copper ammonia rayon or rayon in a treatment liquid containing an epoxy compound, and bonding the epoxy compound to the purified cellulose fiber, natural cellulose fiber, copper ammonia rayon or rayon. Including
The method for producing a modified fiber, wherein the epoxy compound is at least one of resorcinol diglycidyl ether and hydroquinone diglycidyl ether.   The method for producing a modified fiber according to claim 3, wherein the treatment liquid contains a quaternary ammonium salt.