WO2021144854A1

WO2021144854A1 - Fibrillated regenerated cellulose fiber, and fabric using same

Info

Publication number: WO2021144854A1
Application number: PCT/JP2020/000906
Authority: WO
Inventors: 基耶松原; 實松　照剛
Original assignee: 旭化成株式会社
Priority date: 2020-01-14
Filing date: 2020-01-14
Publication date: 2021-07-22
Also published as: EP4092185A1; JPWO2021144854A1; JP7259088B2; EP4092185A4; CN114929962A

Abstract

Provided are a fibrillated regenerated cellulose fiber, and a fabric using the same, the fiber having a characteristic surface texture, softness, and a resilient feeling, being fibrillated by rubbing and tanning treatment in a wet state, and having an excellent surface texture and long-lasting feeling after being water-washed, thereby exhibiting high quality.　Provided are: a regenerated cellulose fiber of which the surface is fibrillated and which has a degree of polymerization of 100-250, and a tensile strength of 1.0-3.0 cN/dtex (exclusive of 1.0 cN/dtex) at the time of drying; a fabric including the regenerated cellulose fiber as a constituent yarn; and a method for producing the regenerated cellulose fiber of which the surface is fibrillated, and the fabric including the regenerated cellulose fiber as a constituent yarn, the method comprising a step for modifying, in an acid solution, the regenerated cellulose fiber into yarn or fabric form, under the conditions of a temperature of 110-150 °C, a pH of 2.6-3.4, and a duration of 10-30 minutes.

Description

Fibrilized regenerated cellulose fibers and fabrics using them

The present invention has a characteristic surface feeling, softness and repulsive texture, is made into fibril by rubbing and softening in a wet state, and has a long-lasting surface feeling and texture against washing with water. The present invention relates to a regenerated cellulose fiber having an excellent high-grade feeling and being made into fibril, and a fabric containing the fiber as a constituent yarn.

Regenerated cellulose fibers include cupraammon rayon, organic solvent method cellulose fibers, etc. All of the cellulose fibers are composed of fibril aggregates mainly composed of cellulose microfibrils, and when rubbed and rubbed in a wet state, the fibers are used. Has the characteristic of being split into fibers in the fiber axis direction.
In order to express the characteristic surface feeling, softness and repulsive texture of clothing manufactured using recycled cellulose fibers, this characteristic is used to make the recycled cellulose fibers that make up the clothing into fibril. Although there are many products that have been made into fibers, there is a problem that when the fibrillated clothing is repeatedly washed with water, the fibrils fall off and the surface feeling and texture are impaired. Further, although there is a prior art document on fibrillation of regenerated cellulose fiber, there is no prior art document that provides a concrete solution to such a problem.

For example, as a processing method for making fibril, Patent Document 1 below discloses a method using an impact during a brushing process or dyeing with a liquid flow dyeing machine. However, since the expression level of fibrils is not constant depending on the dyeing conditions such as dyeing time, bath ratio, fabric speed, and concentration of alkali used, there is a drawback that it is not possible to repeatedly provide products of the same quality. The degree of polymerization of the regenerated cellulose fiber is specified to be 400 or more, and the loss of fibrils due to washing with water is not mentioned.

The following Patent Document 2 discloses fibrillation with an alkaline aqueous solution. However, the degree of polymerization of the regenerated cellulose fiber is specified to be 300 or more, and since the treatment method is treatment in an alkaline aqueous solution, the regenerated cellulose fiber is structurally easily fibrillated only in the alkaline aqueous solution. It is difficult to make fibrils in water washing with a weak alkalinity, and moreover, there is no mention of fibrils falling off due to water washing.

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

Although the following Patent Document 4 does not describe the degree of polymerization of the regenerated cellulose fiber, a method using an acid aqueous solution is disclosed. Patent Document 4 describes a treatment with an acid aqueous 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 dough containing lyocell disclosed in Patent Document 4 is obtained by removing the long fibrils that give the surface of the dough the characteristic surface feeling "Hairy effect" disclosed in the present specification. , The short fibrils on the surface of the fabric are described in Patent Document 4 as a surface finish characterized as a "clean" in which "Hairy effect" is substantially absent, and thus the fibrils disclosed herein. It is different from the regenerated cellulose fiber that has become. Further, Patent Document 4 does not describe the rate of decrease in strength of the dough by the treatment method for removing the long fibrils, and does not mention the removal of fibrils by washing with water.

Japanese Unexamined Patent Publication No. 08-113846 Japanese Unexamined Patent Publication No. 06-166965 Japanese Unexamined Patent Publication No. 11-315474 UK Patent No. 2399094A

In view of the above prior art, the problem to be solved by the present invention is that it has a characteristic surface feeling, softness and a texture with a repulsive feeling, and is made into fibril by rubbing and softening in a wet state. In addition, it is an object of the present invention to provide a high-quality fibrillated regenerated cellulose fiber having excellent surface feeling and long-lasting texture against washing with water, and a fabric using the fiber.

As a result of diligent studies to solve the above problems, the present inventors have found that, rather than modifying the expressed fibrils so that they do not fall off, even if the fibrils fall off, they are modified so that they are re-expressed during washing. We discovered that it was effective, and based on this discovery, we diligently investigated and repeated experiments on a method of modifying fibril so that it would reappear during washing even if it fell off. As a result, the degree of polymerization of the regenerated cellulose fiber was 100 to 100. To complete the present invention, it was unexpectedly found that if the control is set to 250, fibrils are easily expressed only by the weak kneading effect of washing, and the texture is light and soft and repulsive. It has arrived.

That is, the present invention is as follows.
[1] A regenerated cellulose fiber having a degree of polymerization of 100 to 250 and a tensile strength at the time of drying of more than 1.0 cN / dtex and not more than 3.0 cN / dtex, and having a fibrillated surface.
[2] The regenerated cellulose fiber according to the above [1], wherein the regenerated cellulose fiber is an organic solvent method cellulose fiber.
[3] A fabric containing the regenerated cellulose fiber according to the above [1] or [2] as a constituent yarn.
[4] A step of modifying a regenerated cellulose fiber in the form of a thread or a cloth in an acid solution under the conditions of a temperature of 110 ° C. to 150 ° C., a time of 10 minutes to 30 minutes, and a pH of 2.6 to 3.4. The regenerated cellulose fiber according to the above [1] or [2], or the method for producing a fabric according to the above [3].

The fibrillated regenerated cellulose fiber according to the present invention has a characteristic surface feeling, softness and a repulsive texture, and is further fibrillated by rubbing and softening in a wet state. In addition, it is a high-class fiber with excellent surface feeling and long-lasting texture for washing.

It 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 an enlarged photograph which shows the state which the regenerated cellulose fiber is made into fibril.

Hereinafter, embodiments of the present invention will be described in detail.
In one embodiment of the present invention, a regenerated cellulose fiber having a degree of polymerization of 100 to 250 and a tensile strength at the time of drying of more than 1.0 cN / dtex and not more than 3.0 cN / dtex and having a fibrillated surface. Is.
The regenerated cellulose fiber refers to a regenerated cellulose fiber obtained by dissolving and spinning a cellulose raw material such as cupraammon rayon and an organic solvent method cellulose fiber, preferably a cupraammon rayon and an organic solvent method cellulose fiber, and more preferably an organic solvent. Rayon fiber.

The thread form of the regenerated cellulose fiber may be either short fiber or long fiber, but is preferably a long fiber multifilament yarn. The single yarn fineness is not particularly limited, but is preferably 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 counts. The cross-sectional shape of the single yarn is also not particularly limited. The twist is not particularly limited and may be untwisted, false twisted or twisted, and the number of twists is not particularly limited, but the number of additional twists may be 2000 or less. From the viewpoint of texture, untwisted is preferable.

Regarding the compounding with other materials, there is no particular limitation because this embodiment is not affected by other materials, but since the treatment is performed under high pressure as a processing method, the strength of acrylic, diacetate, and hair is reduced and the texture is hardened. , It is not preferable as another material which is a composite partner because it easily causes de-permeability.
The proportion of the regenerated cellulose fiber used in the fabric including the woven fabric and the non-woven fabric is not particularly limited, but in order to exert the desired effect satisfactorily, it is preferably 10% by weight or more, more preferably 20% by weight of the total weight of the fabric. By weight or more, more preferably 30% by weight or more. When the usage ratio is 10% by weight or less, fibrillation is observed, but softness and repulsion are difficult to obtain. The yarn composite method may be any of blended twist, interlaced blended fiber, Taslan blended fiber, covering, blended cotton blended yarn, kneaded strip blended yarn, and finely spun blended yarn.

The fibrilized 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 breaking strength at the time of drying becomes 1.0 cN / dtex or less, and the yarn physical properties required for post-processing until the fabric is made and for use as clothing are not reached. .. On the other hand, if the degree of polymerization is higher than 250, re-expression of fibrils by washing with water cannot be obtained, which is not preferable. The degree of polymerization is measured by a viscosity method using a copper-ammonia solution.

The fabric may be a woven fabric, a warp knit, a circular knit, a flat knit, or a non-woven fabric, and is preferably a woven fabric, a warp knit, a circular knit, a flat knit, and more preferably a woven fabric or a circular knit. The structure and density of the fabric are not particularly limited. As the compounding method when compounding with other materials, any of the compound weaving, the interlacing knitting, the use of the composite yarn, the weft insertion in the warp knitting, and the like may be used.

In the present embodiment, the modification treatment method for adjusting the degree of polymerization of the fibrillated regenerated cellulose fiber to 100 to 250 is not particularly limited. However, by treating the regenerated cellulose fiber having a degree of polymerization of 250 or more and a tensile strength at the time of drying of 2.0 cN / dtex or more in an acid solution, the degree of polymerization is 100 to 250 and the tensile strength at the time of drying is 100 to 250. The modification treatment for adjusting the strength to more than 1.0 cN / dtex to 3.0 cN / dtex or less is particularly preferably used because it is excellent in that the physical properties of the yarn and the degree of polymerization can be easily adjusted. The type of acid used is not particularly limited and may be any of citric acid, malic acid, acetic acid, formic acid, sulfuric acid, nitrate, hydrochloric acid, oxalic acid and the like, but it is preferably less corrosive to metals. More preferably, it is formic acid, citric acid or malic acid. The treatment temperature is preferably 110 ° C. to 150 ° C., more preferably 120 ° C. to 150 ° C., and even more preferably 130 ° C. to 140 ° C. in order to modify the desired degree of polymerization and the desired tensile strength. If the temperature is lower than 110 ° C., long-term treatment is required for modification, and even if the desired degree of polymerization can be modified, the tensile strength is significantly reduced, which is not preferable. Further, when the treatment is performed at a temperature lower than 110 ° C. for a short time, it is necessary to lower the pH, 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, and it is difficult to uniformly modify. In addition, it is not preferable because the quality varies depending on the reforming treatment. On the other hand, if the temperature is 150 ° C. or higher, it is difficult to control the temperature and it is difficult to uniformly reform the temperature, which is not preferable. The treatment pH and treatment time need to be adjusted depending on the regenerated cellulose fiber used, but the treatment pH is preferably 2.6 to 3.4, more preferably 2.8 to 3.2, and the treatment time is 10. It is preferably from 30 minutes to 30 minutes, more preferably from 12 minutes to 28 minutes, and even more preferably from 15 minutes to 25 minutes. For example, when a regenerated cellulose fiber having a degree of polymerization of about 450 to 600 and a tensile strength at the time of drying of 2.0 cN / dtex or more is treated with formic acid, a 76% formic acid concentration is 1.0 g / g. By treating at 130 ° C. for 20 minutes in an acid bath of pH 2.8, which is L, the degree of polymerization is modified to 100 to 250, and the tensile strength at the time of drying is more than 1.0 cN / dtex and 3.0 cN / dtex. Can be kept below. In order to reduce the degree of polymerization to the desired degree of polymerization in a short time and to modify the tensile strength during drying to more than 1.0 cN / dtex and 3.0 cN / dtex or less, a low concentration of acid is used for a short time. It is necessary to carry out the reforming treatment of the above, and for that purpose, a high temperature and high pressure treatment of 110 ° C. or higher is required.

The form of the modification treatment is not particularly limited, but is preferably a thread form or a cloth form, and more preferably a cloth form. The equipment used for processing is not particularly limited in both the thread form and the cloth form, but the thread form is preferably a cheese dyeing machine and a skein dyeing machine, and the cloth form is preferably a liquid flow dyeing machine and an air flow dyeing machine. , Beam dyeing machine, Jigger dyeing machine, Paddle dyeing machine, Drum dyeing machine, Washer dyeing machine, Wins dyeing machine, more preferably liquid flow dyeing machine, air flow dyeing machine.

In order to express fibrils after the modification treatment, a fibrillation treatment in water is required. Therefore, it is necessary to perform the fibrillation treatment at the same time as the modification treatment, or to perform the fibrillation treatment after the modification treatment. There is. The form of the fibrillation treatment is not particularly limited, but is preferably a cloth form. The equipment used for processing is not particularly limited, but preferably a liquid flow dyeing machine, an air flow dyeing machine, a paddle dyeing machine, a drum dyeing machine, a washer dyeing machine, a wins dyeing machine, and more preferably a liquid flow dyeing machine and an air flow dyeing machine. It is a machine. The fibrillation treatment in water is not particularly limited, but for example, the equipment includes a liquid flow dyeing machine, an air flow dyeing machine or a wins dyeing machine, a temperature of 10 to 130 ° C., a cloth speed of 100 m / min or more, and a treatment of 20 minutes or more. It is preferable to use a paddle dyeing machine, a drum dyeing machine or a washer dyeing machine as equipment, and a fibrillation treatment at a temperature of 10 to 130 ° C. and a treatment time of 20 minutes or more. In addition, since it is necessary to prevent the fibrils from being removed after the fibrils are expressed, the texture in a dry state is not processed after the fibrils are expressed, or the texture in a dry state is not performed. When performing the unloading process, for example, a cloth dyeing machine or an air tumbler dryer is used as the equipment, and the fabric speed is 800 m / min or less, the processing time is 60 minutes or less, or a batch type tumbler dryer is used as the equipment. It is preferable to perform a texture-setting treatment under the condition of a treatment time of 60 minutes or less.

The regenerated cellulose fiber of the present embodiment has a tensile strength at the time of drying of more than 1.0 cN / dtex and 3.0 cN / dtex or less, preferably 1.3 cN / dtex or more and 2.5 cN / dtex or less, more preferably 1.5 cN /. It is dtex or more and 2.0 cN / dtex or less. If the tensile strength at the time of drying is 1.0 cN / dtex or less, it will be damaged in various processes until the fabric is manufactured, it will be difficult to obtain a practical fabric, and the repulsive feeling will be impaired, and it will exceed 3.0 cN / dtex. And the softness is impaired.

In the fibrillated regenerated cellulose fiber of the present embodiment, the term "fibrillated" means that a fibril aggregate mainly composed of cellulose microfibrils on the surface constituting the regenerated cellulose fiber is split in the fiber axis direction. The state of being. 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. (Fibrilized state) is shown. FIG. 2 is an enlarged photograph showing a state in which regenerated cellulose fibers are fibrillated, and reference numeral 2 indicates cellulose microfibrils.

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

(1) Degree of polymerization measurement method From the viscosity of a solution of cellulose fibers dissolved in a cuprammonium solution, the following formula:
ηsp / c = K mM
{In the formula, ηsp: specific viscosity, c: fiber concentration (basic molecular weight / 100 ml), Km: constant (5 × 10 ^-4 ), and M: fiber molecular weight} It was carried out by the so-called viscosity method obtained based on the law.

Several types of cellulose fiber samples with different degrees of polymerization are dissolved in copper-ammonia solution in a molecular dispersion manner, and the degree of polymerization is measured with a Nakano-type viscosity tube based on the above formula, and then constant with a tappy-type viscosity tube. The viscosity when dissolved in a copper ammonia solution of a concentration is measured for the above fibrin sample, the relationship between the viscosity and the degree of polymerization is determined in advance, and the viscosity is actually measured by dissolving it in the above constant concentration of copper cheap solution with a tappy type viscosity tube. Then, the degree of polymerization was determined from the relationship table of the viscosity and the degree of polymerization obtained in advance.

The method for measuring the viscosity using the tappy type viscosity tube is as follows. The sample is 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 water content. Weigh 0.1 g of the sample and collect it. Put the wedge and the sample in the tappy type viscosity tube, and then inhale the cuprammonium solution (composition: ammonia: 205 g / L, copper (I) hydroxide (I): 11.0 g / L, sucrose: 10 g / L) into the viscosity tube. Make a stopper. The viscosity tube is set in 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 it into the jacket with the viscosity tube set in the constant temperature water tank. Open the cock of the stopper at the top of the viscometer tube and measure the time for the solution to flow down between the marked lines A and B of the viscometer. The following formula:
V = d / C (tK / t)
{In the formula, V: absolute viscosity (cP), d: specific gravity of solution (g / cm ³ ), C: constant of tappy type viscosity tube, t: flow time (seconds) between marked lines A and B, and K: The flow energy constant of the tappy type viscosity tube. } To determine the absolute viscosity (V). Next, the obtained absolute viscosity value was compared with the above-mentioned relationship table between the viscosity and the degree of polymerization to determine the degree of polymerization.

(2) Tensile strength test method during 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 the Tensilon universal material tester RTC series (manufactured by A & D Co., Ltd.), the sample was pulled at a sample length (thread length) of 200 mm and a tensile speed of 200 mm / min, and the strength at break was measured.

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

(4) Degree of fibrillation Set the sample in the microscope VHX-6000 (manufactured by KEYENCE), and with the magnification of the lens VH-Z20 (manufactured by KEYENCE) 200 times, adjust the brightness and sensitivity conditions. , The sample is photographed by irradiating the sample with light such that the fibril part becomes a white point. Next, the ratio of the area of the white point to the photographed area was calculated, and the degree of fibrillation was evaluated based on the following three-stage evaluation criteria.
○ (Fibrilized): White point area ratio is 10% or more △ (Insufficient fibrillation): White point area ratio is 5% or more and less than 10% × (Not fibrillated): White point Area ratio is less than 5%

(5) Amount of change in fibrillation degree due to washing For the samples before and after washing, the samples are set in the microscope VHX-6000 (manufactured by KEYENCE), and the magnification of the lens VH-Z20 (manufactured by KEYENCE) is 200 times. In this state, while adjusting the brightness and sensitivity conditions, the sample is irradiated with light so that the fibrils become white points in parallel, and the sample is photographed. Next, the ratio of the area of the white point to the photographed area was calculated for the sample before and after washing, and the following formula:
X = AW-BW
{In the formula, X: the amount of change in the degree of fibrillation due to washing (%), AW: the ratio of the area of white points in the sample after washing (%), and BW: the ratio of the area of white points in the sample before washing ( %). } Was used to determine the rate of change in the degree of fibrillation, and the degree of change in the degree of fibrillation was evaluated based on the following three evaluation criteria.
○ (No change in fibrillation): Change amount is -10% or more and less than + 10% × (There is change in fibrillation): Change amount is less than -10% or + 10% or more

(6) Texture For the sample before washing, the texture is evaluated based on the following three evaluation criteria by the sensory test of the touch by repeated gripping work, and for the sample after washing, the evaluation of the sample before washing is performed. Evaluated if the result was 〇 or △:
◯: Excellent softness and resilience Δ: Slightly insufficient softness or resilience ×: Poor softness or resilience

[Example 1]
A cupraammonium rayon 84 dtex / 45 filament having a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried was prepared. This raw yarn was reformed at 130 ° C. for 20 minutes at 1.0 g / L using 76% formic acid in a cheese dyeing machine to bring the degree of polymerization to 200, and modified cuprammonium rayon was obtained. The obtained modified cupraammonium rayon yarn was used as the warp and weft to weave a twill weave having a 2/1 structure having a warp density of 144 threads / 2.54 cm and a weft density of 100 threads / 2.54 cm. The obtained raw machine was scoured and relaxed and fibrillated at 80 ° C. for 20 minutes with a nonionic surfactant of 1 g / L in a liquid flow dyeing machine, and then again in a liquid flow dyeing machine at a dyeing temperature of 60 ° C. for 60 minutes. Cupraammonium 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-based softener, smeared with a pickup of 80%, dried at 150 ° C. for 1 minute, dried at 80 ° C. for 30 minutes, and used in an air tumbler at a speed of 700 m / min. The texture treatment was carried out, and the final set was carried out at 130 ° C. for 1 minute to obtain a dyed woven fabric having a warp density of 153 threads / 2.54 cm and a weft density of 104 threads / 2.54 cm. The degree of polymerization of the cupraammonium rayon 84dtex / 45 filament of the warp taken out from the woven fabric was 200.

[Example 2]
Cupraammonium rayon 84 dtex / 45 filaments with a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried are used for the warp and weft, and the warp density is 144 / 2.54 cm and the weft density is 100 / 2.54 cm. A twill weave with a 2/1 structure was woven. The obtained raw machine 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 flow dyeing machine to bring the degree of polymerization to 200, and then liquid flow dyeing was performed again. Cupraammonium rayon was dyed with a machine at a dyeing temperature of 60 ° C. for 60 minutes, 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-based softener, smeared with a pickup of 80%, dried at 150 ° C. for 1 minute, dried at 80 ° C. for 30 minutes, and used in an air tumbler at a speed of 700 m / min. The texture treatment was carried out, and the final set was carried out at 130 ° C. for 1 minute to obtain a dyed woven fabric having a warp density of 153 threads / 2.54 cm and a weft density of 104 threads / 2.54 cm. The degree of polymerization of the cupraammonium rayon 84dtex / 45 filament of the warp taken out from the woven fabric was 200.

[Example 3]
An organic solvent-based 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. This raw yarn was reformed at 130 ° C. for 20 minutes at 1.0 g / L using 76% formic acid in a cheese dyeing machine to bring the degree of polymerization to 220, and a modified organic solvent method cellulose fiber was obtained. The obtained modified organic solvent method cellulose fiber was used for the warp and weft to weave a plain weave fabric having a warp density of 105 threads / 2.54 cm and a weft density of 89 threads / 2.54 cm. The obtained raw machine was scoured and relaxed and fibrillated at 80 ° C. for 20 minutes with a nonionic surfactant 1 g / L in a liquid flow dyeing machine, and then organically used again in a liquid flow dyeing machine at a dyeing temperature of 60 ° C. for 60 minutes. Dyeing of cellulose fibers by solvent method 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-based softener, smeared with a pickup of 80%, dried at 150 ° C. for 1 minute, dried at 80 ° C. for 30 minutes, and used in an air tumbler at a speed of 700 m / min. The texture treatment was carried out, and the final set was carried out at 130 ° C. for 1 minute to obtain a dyed woven fabric having a warp density of 109 threads / 2.54 cm and a weft density of 92 threads / 2.54 cm. The degree of polymerization of the organic solvent-based cellulose fiber 89dtex / 30 filament of the warp taken out from the woven fabric was 220.

[Example 4]
Using organic solvent-based cellulose fibers 89 dtex / 30 filaments having a degree of polymerization of 490 and a tensile strength of 3.5 cN / dtex when dried as warp and weft, the warp density is 105 / 2.54 cm and the weft density is 89 / 2. A plain weave fabric composed of 54 cm was woven. The obtained raw machine 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 flow dyeing machine to bring the degree of polymerization to 220, and then liquid flow dyeing was performed again. The organic solvent method cellulose fibers were dyed with a machine at a dyeing temperature of 60 ° C. for 60 minutes, 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-based softener, smeared with a pickup of 80%, dried at 150 ° C. for 1 minute, dried at 80 ° C. for 30 minutes, and used in an air tumbler at a speed of 700 m / min. The texture treatment was carried out, and the final set was carried out at 130 ° C. for 1 minute to obtain a dyed woven fabric having a warp density of 109 threads / 2.54 cm and a weft density of 92 threads / 2.54 cm. The degree of polymerization of the organic solvent-based cellulose fiber 89dtex / 30 filament of the warp taken out from the woven fabric was 220.

[Comparative Example 1]
Cupraammonium rayon 84 dtex / 45 filaments with a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried are used for the warp and weft, and the warp density is 144 / 2.54 cm and the weft density is 100 / 2.54 cm. A twill weave with a 2/1 structure was woven. The obtained raw machine was dyed and finished in the same manner as in Example 2 except that the reforming treatment and the fibrillation treatment were not carried out, and the warp density was 153 / 2.54 cm and the weft density was 104 / 2.54 cm. Dyed fabric was obtained. The degree of polymerization of the cupraammonium rayon 84dtex / 45 filament of the warp taken out from the woven fabric was 580.

[Comparative Example 2]
Using organic solvent method cellulose fiber 89dtex / 30 filaments having a degree of polymerization of 490 and a tensile strength of 3.5cN / dtex when dried as warp and weft, the warp density is 109 / 2.54 cm and the weft density is 92 / 2.54 cm. A plain weave woven fabric composed of The obtained raw machine was dyed and finished in the same manner as in Example 4 except that the reforming treatment and the fibrillation treatment were not carried out, and the warp yarn density was 109 yarns / 2.54 cm and the weft yarn density was 92 yarns / 2.54 cm. Dyed fabric was obtained. The degree of polymerization of the organic solvent-based cellulose fiber 89dtex / 30 filament of the warp taken out from the woven fabric was 490.

[Comparative Example 3]
Cupraammonium rayon 84 dtex / 45 filaments with a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried are used for the warp and weft, and the warp density is 144 / 2.54 cm and the weft density is 100 / 2.54 cm. A twill weave with a 2/1 structure was woven. The obtained raw machine was subjected to fibrillation treatment at 80 ° C. for 120 minutes at 40 g / L of sodium hydroxide with a liquid flow dyeing machine, and again at a dyeing temperature of 60 ° C. for 60 minutes with a liquid flow dyeing machine. Was dyed, and then 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-based softener, smeared with a pickup of 80%, dried at 150 ° C. for 1 minute, dried at 80 ° C. for 30 minutes, and used in an air tumbler at a speed of 700 m / min. The texture treatment was carried out, and the final set was carried out at 130 ° C. for 1 minute to obtain a dyed woven fabric having a warp density of 153 threads / 2.54 cm and a weft density of 104 threads / 2.54 cm. The degree of polymerization of the cupraammonium rayon 84dtex / 45 filament of the warp taken out from the woven fabric was 440.

[Comparative Example 4]
Cupraammonium rayon 84 dtex / 45 filaments with a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried are used for the warp and weft, and the warp density is 144 / 2.54 cm and the weft density is 100 / 2.54 cm. A twill weave with a 2/1 structure was woven. The obtained raw machine was subjected to fibrillation treatment at 100 ° C. for 60 minutes at 50 g / L of 75% phosphoric acid in a liquid flow dyeing machine, and cupraammonium was again used in a liquid flow dyeing machine at a dyeing temperature of 60 ° C. for 60 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-based softener, smeared with a pickup of 80%, dried at 150 ° C. for 1 minute, dried at 80 ° C. for 30 minutes, and used in an air tumbler at a speed of 700 m / min. The texture treatment was carried out, and the final set was carried out at 130 ° C. for 1 minute to obtain a dyed woven fabric having a warp density of 153 threads / 2.54 cm and a weft density of 104 threads / 2.54 cm. The degree of polymerization of the cupraammonium rayon 84dtex / 45 filament of the warp taken out from the woven fabric was 400.

[Comparative Example 5]
Cupraammonium rayon 84 dtex / 45 filaments with a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried are used for the warp and weft, and the warp density is 144 / 2.54 cm and the weft density is 100 / 2.54 cm. A twill weave with a 2/1 structure was woven. The obtained raw machine was subjected to fibrillation treatment at 100 ° C. for 60 minutes at 30 g / L of a 35% hydrogen peroxide aqueous solution with a liquid flow dyeing machine, and again at a dyeing temperature of 60 ° C. for 60 minutes with a liquid flow dyeing machine. Cupraammonium 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-based softener, smeared with a pickup of 80%, dried at 150 ° C. for 1 minute, dried at 80 ° C. for 30 minutes, and used in an air tumbler at a speed of 700 m / min. The texture treatment was carried out, and the final set was carried out at 130 ° C. for 1 minute to obtain a dyed woven fabric having a warp density of 153 threads / 2.54 cm and a weft density of 104 threads / 2.54 cm. The degree of polymerization of the cupraammonium rayon 84dtex / 45 filament of the warp taken out from the woven fabric was 180.

[Comparative Example 6]
Cupraammonium rayon 84 dtex / 45 filaments with a degree of polymerization of 580 and a tensile strength of 2.3 cN / dtex when dried are used for the warp and weft, and the warp density is 144 / 2.54 cm and the weft density is 100 / 2.54 cm. A twill weave with a 2/1 structure was woven.
The obtained raw machine was subjected to fibrillation treatment at 130 ° C. for 45 minutes at 6.4 g / L using acetic acid in an air flow dyeing machine, and then cupraammonium was again used in an airflow dyeing machine at a dyeing temperature of 60 ° C. 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-based softener, smeared with a pickup of 80%, dried at 150 ° C. for 1 minute, and used in an air tumbler at 100 ° C. for 30 minutes at a speed of 900 m / min. The texture treatment was carried out, and the final set was carried out at 130 ° C. for 1 minute to obtain a dyed woven fabric having a warp density of 153 threads / 2.54 cm and a weft density of 104 threads / 2.54 cm. The degree of polymerization of the cupraammonium rayon 84dtex / 45 filament of the warp taken out from the woven fabric was 190.

With respect to the woven fabrics obtained in Examples 1 to 4 and Comparative Examples 1 to 6, the sample fabric obtained by repeating the washing according to the washing test method 10 times and the sample fabric not subjected to the washing were determined by the degree of fibrillation and washing. The amount of change in the degree of fibrillation and the texture were evaluated. Further, cuprammonium rayon 84 dtex / 45 filaments and organic solvent method cellulose fibers 89 dtex / 30 filaments obtained by modifying and fibrillating the warp from the woven fabric samples of Examples 1 to 4 were used as woven fabric samples of Comparative Examples 1 to 6. Cupramonium rayon 84 dtex / 45 filaments and organic solvent method cellulose fiber 89 dtex / 30 filaments of the warp yarns that have not been modified or subjected to different fibrillation treatments are taken out from the above, and the tensile strength of the warp yarns during drying is measured. Was carried out. Table 1 below summarizes the materials, modification treatments, and fibril treatments of the sample yarns used in Examples 1 to 4 and Comparative Examples 1 to 6, and Table 2 below shows the evaluation results.

The fabrics using the modified cellulose fibers of Examples 1 to 4 have a good texture with softness and repulsion without any change in fibril feeling due to washing, and have a tensile strength of 1.0 cN / dtex. It turns out that it exceeds. That is, Examples 1 to 4 have a characteristic surface feeling and a softness and a repulsive texture for washing, and are excellent in the durability of the surface feeling and the texture for washing.
On the contrary, the fabrics of Comparative Examples 1 to 6 have a tensile strength of 1.0 cN / dtex or less, fibrils have been removed in the pre-washing stage, or the degree of polymerization exceeds 250 after washing. It can be seen that the fibrils have fallen off and the degree of fibrillation has changed. That is, in Comparative Examples 1 to 6, the change in surface feeling and texture due to washing is large, or the strength as a cloth is not maintained, and holes are generated due to wear during wearing or washing, or before washing. Since the fibrils are removed at the stage of, it is not suitable as a textile product having fibrils that require a good texture.

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

1 A state in which a fibril aggregate mainly composed of cellulose microfibrils is split in the fiber axis direction (a state in which it is fibrillated).
2 Cellulose microfibrils

Claims

A regenerated cellulose fiber having a degree of polymerization of 100 to 250 and a tensile strength at the time of drying of more than 1.0 cN / dtex and less than 3.0 cN / dtex, and having a fibrillated surface.
The regenerated cellulose fiber according to claim 1, wherein the regenerated cellulose fiber is an organic solvent method cellulose fiber.
A fabric containing the regenerated cellulose fiber according to claim 1 or 2 as a constituent yarn.
The step of modifying the regenerated cellulose fiber in the form of a thread or a cloth in an acid solution under the conditions of a temperature of 110 ° C. to 150 ° C., a time of 10 minutes to 30 minutes, and a pH of 2.6 to 3.4 is included. The method for producing a regenerated cellulose fiber according to claim 1 or 2, or a fabric according to claim 3.