JP2020007655A - Fibrillated regenerated cellulose fiber and fabric using the same - Google Patents

Abstract

To provide a regenerated cellulose fiber having texture of particular surface feeling, bulky feeling, and cushioning feeling, fibrillated by rubbing and softening treatment in a moistened state, and excellent in stability of surface feeling and texture to water washing, and a fabric including the fiber.SOLUTION: Provided are a surface-fibrillated regenerated cellulose fiber having a polymerization degree of 100-250, and a tensile strength when dried of 1.0 cN/dtex or more, and a fabric including the regenerated cellulose fiber.SELECTED DRAWING: Figure 1

Description

  The present invention has a texture with a characteristic surface feeling, a swelling feeling and a repulsive feeling, is fibrillated by friction / soft cloth treatment in a wet state, and has a long-lasting surface feeling and a feeling against water washing. The present invention relates to a fibrillated regenerated cellulose fiber having an excellent luxurious feel, and a fabric containing the fiber as a constituent yarn.

The regenerated cellulose fibers include cupraammonium rayon, organic solvent-processed cellulose fibers, and the like.All of the cellulose fibers are composed of fibril aggregates mainly composed of cellulose microfibrils. Has the characteristic of splitting and fibrillating in the fiber axis direction.
In clothing manufactured using regenerated cellulose fibers, in order to develop a texture with a characteristic surface feeling, swelling and resilience, this property is used to fibrillate regenerated cellulose fibers constituting clothing. Although there are a number of products that have been subjected to fibrillation, when fibrillated clothing is repeatedly washed with water, there is a problem that the fibrils fall off and the surface feel and texture are impaired. Further, although there are prior art documents on fibrillation of regenerated cellulose fibers, there is no prior art document that provides a specific solution to such a problem.

  For example, as a processing method for fibrillation, Patent Literature 1 below discloses a method using a brushing treatment or an impact at the time of dyeing by a liquid jet dyeing machine. However, since the expression amount of fibrils is not constant depending on the dyeing conditions such as dyeing time, bath ratio, fabric speed, and the concentration of the used alkali, it has a drawback that products of the same quality cannot be repeatedly provided. The degree of polymerization of the regenerated cellulose fiber is specified to be 400 or more, and no reference is made to the detachment of fibrils by washing with water.

  Patent Document 2 below discloses fibrillation using an aqueous alkali solution. However, the degree of polymerization of the regenerated cellulose fiber is specified to be 300 or more, and the treatment method is a treatment in an alkaline aqueous solution, so that the regenerated cellulose fiber structurally changes easily to fibrillation only in an alkaline aqueous solution. Fibrillation is difficult to occur during washing with a weak alkali, and no mention is made of fibril detachment due to washing with water.

  Patent Document 3 below discloses a method using an aqueous acid solution or an oxidizing agent solution, although there is no description of the degree of polymerization of the regenerated cellulose fiber. The conditions of the treatment method described in Patent Document 3 are compared with the conditions disclosed in the present specification, in which a long-time treatment is performed at a high temperature under normal pressure in a high-concentration acid solution for the purpose of suppressing strength reduction. There is no description about the strength reduction rate by this processing method, and further, there is a description that the strength is reduced by processing under high pressure, which does not completely match the processing conditions disclosed in this specification.

  Patent Document 4 below discloses a method using an aqueous acid solution, although there is no description of the degree of polymerization of regenerated cellulose fibers. Patent Literature 4 describes a treatment with an aqueous acid solution for 30 to 80 minutes aimed at reducing the strength in order to remove long fibrils, and a high-speed tumbling treatment in a dry state. However, the fabric containing lyocell disclosed in Patent Literature 4 is obtained by removing long fibrils that give the surface of the fabric the “Hairy effect” that is the characteristic surface feeling disclosed in the present specification, and The short fibrils present on the surface of the fabric are described in Patent Document 4 as a surface finish characterized as "clean" substantially free of "Hairy effect". It is different from the regenerated cellulose fiber. In addition, Patent Document 4 does not describe at all the strength reduction rate of the dough by the above-described treatment method for removing long fibrils, and further does not mention dropping off of fibrils due to water washing.

JP 08-113846 A JP-A-06-166956 JP-A-11-315474 UK Patent No. 2399094

  In view of the above prior art, the problem to be solved by the present invention is to have a characteristic surface feeling, a swelling feeling and a feeling of rebound, and to be fibrillated by friction / soft cloth treatment in a wet state, Another object of the present invention is to provide a high-grade fibrillated regenerated cellulose fiber having excellent surface feel and long-lasting texture to washing with water, and a fabric using the fiber.

  The present inventors have conducted intensive studies to solve the above-described problems, and rather than modifying the expressed fibrils so that they do not fall off, it is possible to modify the fibrils so that they appear again during washing even if the fibrils fall off. It was found that it was effective, and based on such a finding, even after fibrils were dropped, a method of modifying the fiber so that it reappears during washing was repeatedly studied and as a result of repeated experiments, the polymerization degree of the regenerated cellulose fiber was 100 to 100. If it is controlled to 250, the fibrils are easily expressed only by the weak rubbing effect of the washing, and it is unexpectedly found that the feeling of swelling and resilience with a light feeling in the texture is expressed, and the present invention is completed. It has been reached.

That is, the present invention is as follows.
[1] A regenerated cellulose fiber having a fibrillated surface, having a degree of polymerization of 100 to 250 and a tensile strength when dried of 1.0 cN / dtex or more.
[2] The regenerated cellulose fiber according to [1], wherein the regenerated cellulose fiber is an organic solvent-processed cellulose fiber.
[3] A fabric containing the regenerated cellulose fiber according to [1] or [2] as a constituent yarn.

  The regenerated cellulose fibers which are fibrillated according to the present invention have a characteristic surface feeling, a swelling feeling and a feeling of repulsion, and are further fibrillated by friction / soft cloth treatment in a wet state. Moreover, it is a high-grade fiber excellent in the surface feeling and the durability of the texture for washing.

3 is a photograph of the surface of a woven fabric showing a state in which regenerated cellulose fibers as constituent yarns are fibrillated. It is a photograph which expands and shows the state which the regenerated cellulose fiber is fibrillated.

Hereinafter, embodiments of the present invention will be described in detail.
One embodiment of the present invention is a regenerated cellulose fiber having a fibrillated surface, which has a degree of polymerization of 100 to 250 and a tensile strength when dried of 1.0 cN / dtex or more.
The regenerated cellulose fiber refers to a regenerated cellulose fiber obtained by dissolving and spinning a cellulose material such as cupraammonium rayon or an organic solvent-processed cellulose fiber, and is preferably a cupraammonium rayon or an organic solvent-processed cellulose fiber, and more preferably an organic solvent. It is a method cellulose fiber.

  The yarn form of the regenerated cellulose fiber may be either a short fiber or a long fiber, but is preferably a long fiber multifilament yarn. The single yarn fineness is not particularly limited, but may preferably be 0.5 to 5.0 dtex. The total fineness is not particularly limited, but is preferably 22 to 330 dtex, and the count is not particularly limited, and is preferably 5 to 100 cotton count. There is no particular limitation on the cross-sectional shape of the single yarn. Twisting is also not particularly limited, and it may be non-twisted, false twisted or twisted, and the number of twists is not particularly limited, but preferably not more than 2,000 twists. From the viewpoint of texture, non-twist is preferred.

Regarding the combination with other materials, the present embodiment is not particularly limited because it is not affected by other materials.However, since processing under high pressure is performed as a processing method, acrylic, diacetate, and hair have reduced strength and texture hardening. Therefore, it is not preferable as another material that is a composite partner because it easily causes devitrification.
The proportion of the regenerated cellulose fiber used in the fabric including the woven or knitted fabric or the nonwoven fabric is not particularly limited, but is preferably 10% by weight or more, more preferably 20% by weight of the total weight of the fabric, in order to exhibit the desired effect well. % By weight or more, more preferably 30% by weight or more. When the use ratio is 10% by weight or less, fibrillation is recognized, but a swelling feeling and a resilience are hardly obtained. In addition, as the method of compounding the yarn, any of conjugate twist, interlace blending, Taslan blending, covering, cotton blending, drawing blending, spinning twisting and the like may be used.

  The fibrillated regenerated cellulose fiber of the present embodiment has a degree of polymerization of 100 to 250, preferably 150 to 250, and more preferably 200 to 250. If the degree of polymerization is less than 100, the tensile strength at break during drying will be less than 1.0 cN / dtex, and the yarn properties required for post-processing to fabric and use as clothing will not be achieved. . On the other hand, if the degree of polymerization is higher than 250, it is not preferable because fibrils cannot be re-expressed by washing with water. The polymerization degree is measured by a viscosity method using a copper ammonia solution.

  The fabric may be any of a woven fabric, a warp knitted fabric, a circular knitted fabric, a flat knitted fabric, and a nonwoven fabric, and the structure and density of the fabric are not particularly limited. As a compounding method when compounding with another material, any of cross-weaving, cross-knitting, use of a composite yarn, insertion of a weft in warp knitting, and the like may be used.

  In the present embodiment, the method of modifying the degree of polymerization of the fibrillated regenerated cellulose fiber to 100 to 250 is not particularly limited. However, a method of modifying a degree of polymerization to 100 to 250 by treating a regenerated cellulose fiber having a degree of polymerization of 250 or more and a tensile strength at dryness of 2.0 cN / dtex or more in an acid solution. However, it is particularly preferable because it is excellent in that the physical properties of the yarn and the degree of polymerization are easily adjusted. The treatment temperature is preferably from 110 ° C. to 150 ° C., more preferably from 120 ° C. to 150 ° C., and still more preferably, in order to modify the degree of polymerization to a desired degree of polymerization and maintain the tensile strength upon drying at 1.0 cN / dtex or more. 130 ° C to 140 ° C. If the temperature is lower than 110 ° C., a long-time treatment is required for the modification, and even if the degree of polymerization can be improved to a desired degree, the tensile strength is remarkably reduced, which is not preferable. In addition, when the treatment is performed at a temperature lower than 110 ° C. for a short time, the pH needs to be lowered, and when the treatment is performed at a low pH for a short time, a local decrease in the degree of polymerization and a decrease in the strength occur, so that it is difficult to perform uniform reforming. In addition, it is not preferable because the quality varies for each reforming process. On the other hand, a temperature of 150 ° C. or more is not preferable because it is difficult to control the temperature and it is difficult to perform uniform reforming. The type of acid used is not particularly limited, and may be any of citric acid, malic acid, acetic acid, formic acid, sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, and the like, but is preferably less corrosive to metals, More preferred are formic acid, citric acid and malic acid. The concentration of the acid to be used and the treatment time need to be adjusted depending on the regenerated cellulose fiber to be used. For example, the degree of polymerization is about 450 to 600, and the tensile strength when dried is 2.0 cN / dtex or more. When the regenerated cellulose fiber is treated with formic acid, the degree of polymerization is adjusted to 100 to 100 by treating in a pH 2.8 acid bath having a formic acid concentration of 76% of 1.0 g / L at 130 ° C. for 20 minutes. It can be modified to 250 to keep the tensile strength when dried at 1.0 cN / dtex or more. In order to reduce the degree of polymerization to the target degree of polymerization in a short time and to maintain the tensile strength at the time of drying at 1.0 cN / dtex or more, it is necessary to use a low-concentration acid and perform a short-time modification treatment. For that purpose, a high-temperature and high-pressure treatment of 110 ° C. or more is required.

  There are no particular restrictions on the form in which the modification is to be made, but the form is preferably a thread form or a cloth form, more preferably a cloth form. The equipment used for processing is not particularly limited in both the thread form and the fabric form, but in the thread form, preferably a cheese dyeing machine, a skein dyeing machine, and in the fabric form, preferably a liquid jet dyeing machine or an air jet dyeing machine. A beam dyeing machine, a jigger dyeing machine, a paddle dyeing machine, a drum dyeing machine, a washer dyeing machine, a wins dyeing machine, more preferably a liquid jet dyeing machine and an air jet dyeing machine.

  In order to express fibrils after the modification, a softening treatment in water is required.Therefore, the modification treatment in the acid solution is performed by the softening treatment, or the modification treatment in the acid solution is performed. It is necessary to perform a soft cloth treatment in water later. The method of the soft cloth treatment in water is not particularly limited. For example, as a facility, a liquid dyeing machine, an airflow dyeing machine or a wins dyeing machine, a temperature of 10 to 130 ° C., a speed of the fabric of 100 m / min or more, 20 minutes or more Or a soft cloth treatment with a paddle dyeing machine, a drum dyeing machine or a washer dyeing machine as a facility at a temperature of 10 to 130 ° C. for a processing time of 20 minutes or more. In addition, since it is necessary to prevent the fibrils from being removed after the fibrils are expressed, do not carry out the softening treatment in a dry state after the fibrils are expressed, or When performing the cloth treatment, for example, using an airflow dyeing machine or an air tumbler dryer as the equipment, processing speed of the fabric at 800 m / min or less, 60 minutes or less, or using a batch tumbler dryer as the equipment The soft cloth treatment under the condition of the treatment time of 60 minutes or less is preferable.

  The regenerated cellulose fiber of the present embodiment has a dry tensile strength of 1.0 cN / dtex or more, preferably 1.3 cN / dtx, and more preferably 1.5 cN / dtx. If the tensile strength at the time of drying is less than 1.0 cN / dtex, it will be damaged in various steps until the fabric is manufactured, and it is difficult to obtain a practical fabric.

  In the fibrillated regenerated cellulose fiber of the present embodiment, the term "fibrillated" means that the fibril aggregate mainly composed of cellulose microfibrils on the surface constituting the regenerated cellulose fiber is split in the fiber axis direction. State. FIG. 1 is a photograph of the surface of a woven fabric showing a state in which regenerated cellulose fibers as constituent yarns are fibrillated, and reference numeral 1 is a state in which a fibril aggregate mainly composed of cellulose microfibrils is split in the fiber axis direction. (Fibrillated state). FIG. 2 is an enlarged photograph showing a state where the regenerated cellulose fibers are fibrillated, and reference numeral 2 indicates cellulose microfibrils.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Various performance evaluations of each yarn or fabric in the examples were performed by the following methods.

(1) Method of measuring degree of polymerization From the viscosity of a solution obtained by dissolving cellulose fibers in a copper ammonia solution,
ηsp / c = KmM
In the formula, ηsp: specific viscosity, c: cellulose concentration (basic molecular mole number / 100 ml), Km: constant number (5 × 10 ⁻⁴ ), and M: molecular weight of fibrous material. It was carried out by the so-called viscosity method, which was determined based on the law.

  Dissolve several types of cellulose fiber samples with different degrees of polymerization in a copper ammonia solution in a molecular dispersion form, measure the degree of polymerization with a Nakano type viscosity tube based on the above formula, and then keep it constant with a tappy type viscosity tube. The viscosity when dissolved in a copper ammonia solution with a concentration is measured for the above fibrous sample, the relationship between the viscosity and the degree of polymerization is determined in advance, and the viscosity is measured by dissolving it in a copper concentration solution with a constant concentration using a tappy type viscosity tube. Then, the degree of polymerization was determined from a previously obtained relationship table between the viscosity and the degree of polymerization.

The method of measuring the viscosity using a tappy type viscosity tube is as follows. The sample is left in a constant temperature and humidity room at a temperature of 20 ° C. and a humidity of 65% for 24 hours or more to equilibrate the moisture content. Weigh 0.1 g of sample and collect. A wedge and a sample are put into a tappy type viscosity tube, and then a copper ammonia solution (composition: ammonia: 205 g / L, copper (I) hydroxide: 11.0 g / L, sucrose: 10 g / L) is sucked into the viscosity tube. Stopper and stopper. The viscosity tube is set on a rotating device and rotated at a speed of 3 RPM for 30 minutes to dissolve the sample. The viscosity tube is removed from the rotating device and immersed in a constant temperature water bath at 20 ° C. for 5 minutes. Remove the stopper at the bottom of the viscosity tube, and insert the viscosity tube into the jacket set in the water bath. Open the cock of the stopper at the top of the viscosity tube, and measure the time for the solution to flow between the marked lines A and B of the viscometer. The following formula:
V = d / C (t−K / t)
In the formula, V: absolute viscosity (cP), d: specific gravity of the solution (g / cm ³ ), C: constant number of the tappy type viscosity tube, t: flow time (second) between the marked lines A and B, and K: Flow energy constant of the tappy type viscosity tube. The absolute viscosity (V) was determined by｝. Next, the degree of polymerization was determined by comparing the determined value of the absolute viscosity with the above-mentioned relationship table between the viscosity and the degree of polymerization.

(2) Test Method for Tensile Strength at Drying The sample was left in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 65% for 24 hours or more to equilibrate the moisture content. Using a Tensilon universal material testing machine RTC series (manufactured by A & D), the sample was pulled at a sample length (yarn length) of 200 mm and a pulling speed of 200 mm / min, and the strength at break was measured.

(3) Washing test method It was carried out according to JIS L0217-103 method. A detergent for clothing is added and dissolved at a rate of 2 g in 1 L of water at a liquid temperature of 40 ° C., and this is used as a washing liquid. A sample thread and a load cloth are put into the washing liquid so that the bath ratio becomes 1:30, and the operation is started. After washing for 5 minutes, dehydrated, then rinsed at room temperature for 2 minutes at the same bath ratio, dehydrated, rinsed again at room temperature for 2 minutes at the same bath ratio, dehydrated, and finished washing once. I do. The drying method was tumbler drying at 80 ° C. for 20 minutes.

(4) Degree of fibrillation The degree of fibrillation was evaluated based on the following two-grade evaluation criteria by visual judgment under a microscope.
：: Fibril is expressed X: Fibril is not expressed

(5) Degree of fibrillation after washing The degree of fibrillation before and after washing was evaluated based on the following two-grade evaluation criteria by visual judgment in a state enlarged by a microscope:
：: Fibrils are not dropped. X: Fibrils are dropped.

(6) Texture The texture was evaluated by a sensory test by touch based on the following three criteria:
：: Soft and excellent resilience △: Softness and resilience are slightly insufficient X: Softness and resilience are inferior.

[Example 1]
Cupra ammonium rayon 84dtex / 45 filament having a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried was prepared. This yarn was subjected to a modification treatment at 130 ° C. for 20 minutes at 76 ° C. and 1.0 g / L using a cheese dyeing machine to give a polymerization degree of 200, and a modified cupra ammonium rayon was obtained. Using the obtained modified cupra ammonium rayon as the warp and the weft, a 2/1 design twill fabric having a warp density of 144 / 2.54 cm and a weft density of 100 / 2.54 cm was woven. The obtained greige fabric was subjected to scouring relaxation and fibrillation treatment at 80 ° C. for 20 minutes with a nonionic surfactant 1 g / L using a liquid jet dyeing machine, and then again for 60 minutes at a dyeing temperature of 60 ° C. with a liquid jet dyeing machine. Cupra ammonium rayon was stained, and then soaped at 80 ° C. for 10 minutes. After dyeing and drying, it is impregnated with an aqueous solution containing 1% by weight of a silicone softening agent, printed with 80% pickup, dried at 150 ° C. for 1 minute, and air tumbler at 80 ° C. for 30 minutes at a speed of 700 m / min. The texture was set, and the final setting was performed at 130 ° C. for 1 minute to obtain a dyed fabric having a warp density of 153 yarns / 2.54 cm and a weft yarn density of 104 yarns / 2.54 cm. The degree of polymerization of the warp cupraammonium rayon 84 dtex / 45 filaments removed from the woven fabric was 200.

[Example 2]
Using a cupraammonium rayon 84dtex / 45 filament having a degree of polymerization of 580 and a dry tensile strength of 2.3 cN / dtex for warp and weft, and having a warp density of 144 / 2.54 cm and a weft density of 100 / 2.54 cm. The twill woven fabric having a 2/1 texture was woven. The obtained green fabric was subjected to a reforming treatment and a fibrillation treatment at 130 ° C. for 20 minutes at 76 g of formic acid using a liquid dyeing machine at 76% formic acid to a polymerization degree of 200, and then liquid dyeing again. Cupra ammonium rayon was dyed at a dyeing temperature of 60 ° C. for 60 minutes in a machine, and then soaped at 80 ° C. for 10 minutes. After dyeing and drying, it is impregnated with an aqueous solution containing 1% by weight of a silicone softening agent, printed with 80% pickup, dried at 150 ° C. for 1 minute, and air tumbler at 80 ° C. for 30 minutes at a speed of 700 m / min. The texture was set, and the final setting was performed at 130 ° C. for 1 minute to obtain a dyed fabric having a warp density of 153 yarns / 2.54 cm and a weft yarn density of 104 yarns / 2.54 cm. The degree of polymerization of the warp cupraammonium rayon 84 dtex / 45 filaments removed from the woven fabric was 200.

[Example 3]
An organic solvent-processed cellulose fiber 89 dtex / 30 filament having a degree of polymerization of 490 and a tensile strength of 3.5 cN / dtex when dried was prepared. The raw yarn was subjected to a modification treatment at 130 ° C. for 20 minutes at 76 ° C. and 76% formic acid at 130 ° C. for 20 minutes using a cheese dyeing machine to obtain a modified organic solvent-based cellulose fiber. Using the obtained modified organic solvent-processed cellulose fiber as the warp and the weft, a flat-woven fabric having a warp density of 105 / 2.54 cm and a weft density of 89 / 2.54 cm was woven. The obtained greige fabric was subjected to scouring relaxation and fibrillation treatment at 80 ° C. for 20 minutes with a nonionic surfactant 1 g / L by a liquid jet dyeing machine, and then again organically at a dyeing temperature of 60 ° C. for 60 minutes by a liquid jet dyeing machine. The solvent-processed cellulose fiber was dyed, and then soaped at 80 ° C. for 10 minutes. After dyeing and drying, it is impregnated with an aqueous solution containing 1% by weight of a silicone softening agent, printed with 80% pickup, dried at 150 ° C. for 1 minute, and air tumbler at 80 ° C. for 30 minutes at a speed of 700 m / min. The texture was set and the final setting was performed at 130 ° C. for 1 minute to obtain a dyed fabric having a warp density of 109 yarns / 2.54 cm and a weft yarn density of 92 yarns / 2.54 cm. The polymerization degree of the organic solvent-processed cellulose fiber 89 dtex / 30 filament of the warp removed from the woven fabric was 220.

[Example 4]
Using, as a warp and a weft, an organic solvent-processed cellulose fiber 89 dtex / 30 filament having a degree of polymerization of 490 and a tensile strength of 3.5 cN / dtex as a warp and a weft, a warp density of 105 / 2.54 cm and a weft density of 89/2. A plain-textile woven fabric composed of 54 cm was woven. The obtained greige was subjected to a modification treatment and a fibrillation treatment at 130 ° C. for 20 minutes at 1.0 g / L using 76% formic acid in a liquid jet dyeing machine to adjust the degree of polymerization to 220, followed by liquid jet dyeing again. The dyeing of the cellulose fiber by the organic solvent method was performed at a dyeing temperature of 60 ° C. for 60 minutes, and then the soaping was performed at 80 ° C. for 10 minutes. After dyeing and drying, it is impregnated with an aqueous solution containing 1% by weight of a silicone softening agent, printed with 80% pickup, dried at 150 ° C. for 1 minute, and air tumbler at 80 ° C. for 30 minutes at a speed of 700 m / min. The texture was set and the final setting was performed at 130 ° C. for 1 minute to obtain a dyed fabric having a warp density of 109 yarns / 2.54 cm and a weft yarn density of 92 yarns / 2.54 cm. The polymerization degree of the organic solvent-processed cellulose fiber 89 dtex / 30 filament of the warp removed from the woven fabric was 220.

[Comparative Example 1]
A cupraammonium rayon 84dtex / 45 filament having a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried is used for warp and weft, and has a warp density of 144 yarns / 2.54 cm and a weft density of 100 yarns / 2.54 cm. The twill woven fabric having a 2/1 texture was woven. The obtained greige fabric was dyed and finished in the same manner as in Example 2 except that the modification treatment and the fibrillation treatment were not performed, and the warp density was 153 yarns / 2.54 cm and the weft yarn density was 104 yarns / 2.54 cm. Was obtained. The polymerization degree of the warp cupra ammonium rayon 84 dtex / 45 filaments removed from the woven fabric was 580.

[Comparative Example 2]
Using, as a warp and a weft, an organic solvent-processed cellulose fiber 89 dtex / 30 filament having a degree of polymerization of 490 and a tensile strength of 3.5 cN / dtex as a warp and a weft, a warp density of 109 / 2.54 cm and a weft density of 92 / 2.54 cm Was woven. The obtained greige fabric was dyed and finished in the same manner as in Example 4 except that the modification treatment and the fibrillation treatment were not performed, and the warp density was 109 yarns / 2.54 cm and the weft yarn density was 92 yarns / 2.54 cm. Was obtained. The degree of polymerization of the organic solvent-processed cellulose fiber 89 dtex / 30 filament of the warp removed from the woven fabric was 490.

[Comparative Example 3]
A cupraammonium rayon 84dtex / 45 filament having a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried is used for warp and weft, and has a warp density of 144 yarns / 2.54 cm and a weft density of 100 yarns / 2.54 cm. The twill woven fabric having a 2/1 texture was woven. The obtained green fabric was subjected to a fibrillation treatment at 40 ° C. for 120 minutes with 40 g / L of sodium hydroxide using a liquid jet dyeing machine, and again for 60 minutes at a dyeing temperature of 60 ° C. with a liquid jet dyeing machine. Was carried out, and then soaping was carried out at 80 ° C. for 10 minutes. After dyeing and drying, it is impregnated with an aqueous solution containing 1% by weight of a silicone softening agent, printed with 80% pickup, dried at 150 ° C. for 1 minute, and air tumbler at 80 ° C. for 30 minutes at a speed of 700 m / min. The texture was set, and the final setting was performed at 130 ° C. for 1 minute to obtain a dyed fabric having a warp density of 153 yarns / 2.54 cm and a weft yarn density of 104 yarns / 2.54 cm. The polymerization degree of the cupra ammonium rayon 84 dtex / 45 filament of the warp removed from the woven fabric was 440.

[Comparative Example 4]
A cupraammonium rayon 84dtex / 45 filament having a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried is used for warp and weft, and has a warp density of 144 yarns / 2.54 cm and a weft density of 100 yarns / 2.54 cm. The twill woven fabric having a 2/1 texture was woven. The obtained green fabric was subjected to fibrillation treatment at 50 ° C. for 60 minutes with 75% phosphoric acid at 50 g / L using a liquid jet dyeing machine, and again for 60 minutes at a dyeing temperature of 60 ° C. with a liquid jet dyeing machine. Rayon was dyed, and then soaped at 80 ° C. for 10 minutes. After dyeing and drying, it is impregnated with an aqueous solution containing 1% by weight of a silicone softening agent, printed with 80% pickup, dried at 150 ° C. for 1 minute, and air tumbler at 80 ° C. for 30 minutes at a speed of 700 m / min. The texture was set, and the final setting was performed at 130 ° C. for 1 minute to obtain a dyed fabric having a warp density of 153 yarns / 2.54 cm and a weft yarn density of 104 yarns / 2.54 cm. The degree of polymerization of the warp cupraammonium rayon 84 dtex / 45 filaments removed from the woven fabric was 400.

[Comparative Example 5]
A cupraammonium rayon 84dtex / 45 filament having a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried is used for warp and weft, and has a warp density of 144 yarns / 2.54 cm and a weft density of 100 yarns / 2.54 cm. The twill woven fabric having a 2/1 texture was woven. The obtained greige fabric was subjected to a fibrillation treatment with a 35% aqueous hydrogen peroxide solution at 30 g / L at 100 ° C. for 60 minutes using a liquid jet dyeing machine, and again at a dyeing temperature of 60 ° C. for 60 minutes using a liquid jet dyeing machine. Cupra ammonium rayon was stained, and then soaped at 80 ° C. for 10 minutes. After dyeing and drying, it is impregnated with an aqueous solution containing 1% by weight of a silicone softening agent, printed with 80% pickup, dried at 150 ° C. for 1 minute, and air tumbler at 80 ° C. for 30 minutes at a speed of 700 m / min. The texture was set, and the final setting was performed at 130 ° C. for 1 minute to obtain a dyed fabric having a warp density of 153 yarns / 2.54 cm and a weft yarn density of 104 yarns / 2.54 cm. The polymerization degree of the cupra ammonium rayon 84 dtex / 45 filament of the warp removed from the woven fabric was 180.

[Comparative Example 6]
A cupraammonium rayon 84dtex / 45 filament having a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried is used for warp and weft, and has a warp density of 144 yarns / 2.54 cm and a weft density of 100 yarns / 2.54 cm. The twill woven fabric having a 2/1 texture was woven.
The obtained green fabric was subjected to a fibrillation treatment at 130 ° C. for 45 minutes at 6.4 g / L with acetic acid using an air current dyeing machine, and then again for 360 minutes at a dyeing temperature of 60 ° C. using an air current dyeing machine for 360 minutes. Rayon was dyed, and then soaped at 80 ° C. for 10 minutes. After dyeing and drying, it is impregnated with an aqueous solution containing 1% by weight of a silicone softener, printed with an 80% pickup, dried at 150 ° C. for 1 minute, and dried at 100 ° C. for 30 minutes at an air tumbler at a speed of 900 m / min. The texture was set, and the final setting was performed at 130 ° C. for 1 minute to obtain a dyed fabric having a warp density of 153 yarns / 2.54 cm and a weft yarn density of 104 yarns / 2.54 cm. The degree of polymerization of the warp yarn cupra ammonium rayon 84 dtex / 45 filaments removed from the woven fabric was 150.

  For the woven fabrics obtained in Examples 1 to 4 and Comparative Examples 1 to 6, the degree of fibrillation and texture of the sample cloth obtained by repeating the washing by the above-mentioned washing test method 10 times and the sample cloth not subjected to the washing were measured. An evaluation was performed. Further, 84 dtex / 45 filaments of cupraammonium rayon and 89 dtex / 30 filaments of organic solvent-processed cellulose fibers, which had been subjected to the warp modification treatment and fibrillation treatment from the woven fabric samples of Examples 1 to 4, were used for the woven fabric samples of Comparative Examples 1 to 6. From the untreated or different fibrillation-treated cuprammonium rayon 84 dtex / 45 filament and the organic solvent-processed cellulose fiber 89 dtex / 30 filament, respectively, and measure the tensile strength of the warp when dried. Was carried out. Table 1 below summarizes the material, modification treatment, and fibril treatment of the sample yarns used in Examples 1 to 4 and Comparative Examples 1 to 5, and Table 2 below shows the evaluation results.

In the fabrics using the modified cellulose fibers of Examples 1 to 4, there was no change in the fibril feeling due to washing, the soft and swelling feeling was good, and the tensile strength was 1.0 cN / dtex or more. It turns out that it is. That is, Examples 1 to 4 have a texture with a distinctive surface feeling, a swelling feeling and a repulsive feeling during washing, and are excellent in the surface feeling and the durability of the washing feeling.
On the other hand, the fabrics of Comparative Examples 1 to 6 have a degree of polymerization of more than 250 and have a poor fibril feeling before or after washing, and a tensile strength of less than 1.0 cN / dtex, or It can be seen that fibrils have been removed at the stage. That is, in Comparative Examples 1 to 6, the change in the surface feeling and the feeling due to washing is large, or the strength as a fabric is not maintained, or the fibrils are removed at the stage before washing, so that the good feeling is obtained. Not suitable as a textile having the required fibrils.

  According to the present invention, it has a texture with a characteristic surface feeling, a swelling feeling, and a repulsive feeling, is easily fibrillated by friction / soft cloth treatment in a wet state, and maintains a surface feeling and a feeling against water washing. The present invention has industrial applicability since it is possible to provide a high-quality regenerated cellulose fiber having excellent properties and a fabric using the fiber.

1 Fibril aggregate mainly composed of cellulose microfibrils split in the fiber axis direction (fibrillated state)
2 Cellulose microfibrils

Claims (3)

  A regenerated cellulose fiber having a fibrillated surface, having a degree of polymerization of 100 to 250 and a tensile strength at the time of drying of 1.0 cN / dtex or more.   The regenerated cellulose fiber according to claim 1, wherein the regenerated cellulose fiber is an organic solvent-processed cellulose fiber.   A fabric comprising the regenerated cellulose fiber according to claim 1 or 2 as a constituent yarn.