JP7259088B2 - Fibrillated regenerated cellulose fiber and fabric using the same - Google Patents

Description

The present invention has a characteristic surface feel, softness, and resilience texture, is fibrillated by friction and soft cloth treatment in a wet state, and maintains the surface texture and texture to water washing. The present invention relates to a fibrillated regenerated cellulose fiber having an excellent high-class feeling, and a fabric containing the fiber as a constituent yarn.

Regenerated cellulose fibers include cuprammonium rayon, organic solvent method cellulose fibers, etc. All cellulose fibers are composed of fibril aggregates mainly composed of cellulose microfibrils. has the characteristic of splitting and fibrillating in the direction of the fiber axis.
In order to make clothing manufactured using regenerated cellulose fibers express a characteristic texture, softness, and resilience, this characteristic is used to fibrillate the regenerated cellulose fibers that make up the clothing. However, 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 damaged. In addition, although there are prior art documents related to fibrillation of regenerated cellulose fibers, there are no prior art documents that provide specific solutions to such problems.

For example, as a processing method for fibrillating, the following Patent Document 1 discloses a method using a raising treatment or an impact during dyeing by a jet dyeing machine. However, since the amount of fibril expression is not constant depending on the dyeing conditions such as dyeing time, bath ratio, fabric speed, concentration of alkali used, etc., it has the disadvantage that it is not possible to repeatedly provide products with the same quality. The degree of polymerization of regenerated cellulose fibers is specified to be 400 or more, and there is no mention of detachment of fibrils due to water washing.

Patent Document 2 below discloses fibrillation with an alkaline aqueous solution. However, the degree of polymerization of regenerated cellulose fibers is defined as 300 or more, and the treatment method is treatment in an alkaline aqueous solution. It is difficult to fibrillate in weakly alkaline water washing, and moreover, there is no mention of detachment of fibrils due to water washing.

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

Patent Document 4 below does not describe the degree of polymerization of regenerated cellulose fibers, but discloses a method using an acid aqueous solution. Patent Document 4 describes a treatment with an aqueous acid solution for 30 to 80 minutes to remove long fibrils in order to reduce the strength, and a high-speed tumbling treatment in a dry state. However, the lyocell-containing fabric disclosed in US Pat. , the short fibrils present on the surface of the fabric are described in US Pat. It is different from the regenerated cellulose fibers that are hardened. In addition, Patent Document 4 does not mention at all about the strength reduction rate of the fabric due to the treatment method for removing the long fibrils, and furthermore, does not refer to the falling off of the fibrils due to washing with water.

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

In view of the above prior art, the problem to be solved by the present invention is to have a characteristic surface feeling, softness, and resilience texture, and to fibrillate by friction and soft cloth treatment in a wet state, Another object of the present invention is to provide a fibrillated regenerated cellulose fiber that has a high-class feel with excellent durability of surface feeling and texture to water washing, and a fabric using the fiber.

The present inventors have made intensive studies to solve the above problems, and found that rather than modifying the fibrils so that they do not fall off, it is preferable to modify the fibrils so that even if they fall off, they will reappear during washing. On the basis of this discovery, we conducted intensive studies and repeated experiments on a method for modifying the fibril so that it reappears during washing even if the fibril has fallen off. It was unexpectedly found that when controlled to 250, fibrils are easily expressed only by weak rubbing effect of washing, and softness and resilience with a light feeling are expressed in the texture, and the present invention is completed. It has arrived.

That is, the present invention is as follows.
[1] A regenerated cellulose fiber having a fibrillated surface, having a polymerization degree of 100 to 250 and a dry tensile strength of more than 1.0 cN/dtex to 3.0 cN/dtex or less.
[2] The regenerated cellulose fiber according to [1] above, wherein the regenerated cellulose fiber is an organic solvent method cellulose fiber.
[3] A fabric comprising the regenerated cellulose fiber according to [1] or [2] above as constituent yarn.
[4] A step of modifying regenerated cellulose fibers in the form of thread or fabric in an acid solution at a temperature of 110°C to 150°C for 10 minutes to 30 minutes and a pH of 2.6 to 3.4. The method for producing the regenerated cellulose fiber according to [1] or [2], or the fabric according to [3].

The fibrillated regenerated cellulose fiber according to the present invention has a characteristic surface feeling, softness, and resilience texture, and is fibrillated by friction and soft cloth treatment in a wet state, In addition, it is a high-class fiber with excellent durability of surface feeling and texture after washing.

1 is a photograph of the surface of a fabric showing a fibrillated state of regenerated cellulose fibers as constituent yarns. 1 is an enlarged photograph showing a state in which regenerated cellulose fibers are fibrillated.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
One embodiment of the present invention is a regenerated cellulose fiber with a fibrillated surface, which has a polymerization degree of 100 to 250 and a dry tensile strength of more than 1.0 cN/dtex and 3.0 cN/dtex or less. is.
The regenerated cellulose fiber refers to a regenerated cellulose fiber obtained by dissolving and spinning a cellulose raw material such as cupra-ammonium rayon and organic solvent-processed cellulose fiber, preferably cupra-ammonium rayon and organic solvent-processed cellulose fiber, more preferably organic solvent. It is a legal cellulose fiber.

The filament form of the regenerated cellulose fibers may be either short fibers or long fibers, but preferably multifilament yarns of long fibers. Although the fineness of single yarn is not particularly limited, it is preferably 0.5 to 5.0 dtex. Although the total fineness is not particularly limited, it is preferably 22 to 330 dtex, and the count is also not particularly limited, preferably 5 to 100 cotton count. The cross-sectional shape of the single yarn is also not particularly limited. Twisting is also not particularly limited, and may be untwisted, false twisted, or twisted. The number of twists is also not particularly limited, but preferably 2,000 additional twists or less. From the viewpoint of texture, non-twisting is preferred.

Regarding the combination with other materials, this embodiment is not affected by other materials, so there is no particular limitation. , loss of transmission, etc., are likely to occur.
The ratio of the regenerated cellulose fiber used in the fabric including woven and knitted fabrics and non-woven fabrics is not particularly limited, but in order to exhibit the desired effect well, 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. If the use ratio is 10% by weight or less, fibrillation is observed, but it is difficult to obtain softness and resilience. Yarns may be combined by any of plied twist, interlaced mixed fiber, taslan mixed fiber, covering, mixed cotton blended spinning, draw blended spinning, spun mixed twisting, and the like.

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

The fabric may be a woven fabric, a warp knitted fabric, a circular knitted fabric, a flat knitted fabric, or a non-woven fabric, preferably a woven fabric, a warp knitted fabric, a circular knitted fabric, or a flat knitted fabric, and more preferably a woven fabric or a circular knitted fabric. The texture and density of the fabric are also not particularly limited. Composite methods for compositing with other materials include mixed weaving, mixed knitting, use of composite yarns, insertion of weft yarns in warp knitting, and the like.

In the present embodiment, the modification treatment method for adjusting the degree of polymerization of fibrillated regenerated cellulose fibers to 100 to 250 is not particularly limited. However, regenerated cellulose fibers having a polymerization degree of 250 or more and a dry tensile strength of 2.0 cN/dtex or more are treated in an acid solution to increase the polymerization degree to 100 to 250 and dry tensile strength. A modification treatment that adjusts the strength to more than 1.0 cN/dtex and less than or equal to 3.0 cN/dtex is excellent in that it facilitates adjustment of the yarn physical properties and degree of polymerization, and is particularly preferably used. The type of acid to be 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, etc., but is preferably less corrosive to metals. More preferred are formic acid, citric acid and malic acid. The treatment temperature is preferably 110° C. to 150° C., more preferably 120° C. to 150° C., still more preferably 130° C. to 140° C., in order to modify the desired degree of polymerization and tensile strength. If the temperature is lower than 110° C., a long treatment time is required for the modification, and even if the desired degree of polymerization can be obtained, the tensile strength is significantly lowered, which is not preferable. In addition, in the case of short-time treatment at less than 110 ° C., it is necessary to lower the pH, and treatment at a short time and low pH causes a local decrease in the degree of polymerization and a decrease in strength, making uniform modification difficult. In addition, it is not preferable because the quality varies for each modification treatment. On the other hand, a temperature of 150° C. or higher is not preferable because it is difficult to control the temperature and uniform reforming is difficult. 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 minutes to 30 minutes, more preferably 12 minutes to 28 minutes, even more preferably 15 minutes to 25 minutes. For example, when a regenerated cellulose fiber having a polymerization degree of about 450 to 600 and a dry tensile strength of 2.0 cN/dtex or more is treated with formic acid, the formic acid concentration of 76% is 1.0 g/ The degree of polymerization is modified from 100 to 250 by treatment at 130 ° C. for 20 minutes in an acid bath of pH 2.8, which is L, and the dry tensile strength is greater 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 modify the dry tensile strength to more than 1.0 cN / dtex and 3.0 cN / dtex or less, use a low-concentration acid for a short time. For this purpose, high temperature and high pressure treatment at 110° C. or higher is required.

The form of modification treatment is not particularly limited, but is preferably in the form of yarn or cloth, and more preferably in the form of cloth. The equipment used for processing is not particularly limited for both the yarn form and the fabric form, but in the yarn form, cheese dyeing machines and skein dyeing machines are preferable, and in the fabric form, jet dyeing machines and air jet dyeing machines are preferable. , beam dyeing machine, jigger dyeing machine, paddle dyeing machine, drum dyeing machine, washer dyeing machine, wince dyeing machine, more preferably liquid jet dyeing machine, air jet dyeing machine.

In order to develop 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 fibrillation treatment is not particularly limited, but the form of fabric is preferred. The equipment used for processing is not particularly limited, but preferably jet dyeing machine, jet dyeing machine, paddle dyeing machine, drum dyeing machine, washer dyeing machine, wince dyeing machine, more preferably liquid jet dyeing machine, jet dyeing machine. The fibrillation treatment in water is not particularly limited, but for example, equipment includes a jet dyeing machine, a jet dyeing machine or a wince dyeing machine, a temperature of 10 to 130 ° C., a fabric speed of 100 m / min or more, and a treatment of 20 minutes or more. A fibrillation treatment with a paddle dyeing machine, a drum dyeing machine or a washer dyeing machine as equipment, a temperature of 10 to 130° C., and a treatment time of 20 minutes or longer is preferable. In addition, since it is necessary to prevent the fibrils from being removed after the fibrils are developed, it is necessary to either not perform a texture-improving treatment in a dry state after the fibrils are developed, or to reduce the texture in a dry state. When carrying out the treatment, for example, a fabric speed of 800 m / min or less and a processing time of 60 minutes or less using an air current dyeing machine or an air tumbler dryer as equipment, or a batch type tumbler dryer as equipment. It is preferable to carry out a texture-finishing treatment under the condition that the treatment time is 60 minutes or less.

The regenerated cellulose fiber of the present embodiment has a dry tensile strength 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/dtex. dtex or more and 2.0 cN/dtex or less. If the tensile strength when dry is 1.0 cN/dtex or less, it will be damaged in various processes until the fabric is manufactured, making it difficult to obtain a practical fabric and impairing the resilience, and exceeding 3.0 cN/dtex. and the softness is impaired.

The term “fibrillated” in the fibrillated regenerated cellulose fiber of the present embodiment means that fibril aggregates mainly composed of cellulose microfibrils on the surface constituting the regenerated cellulose fiber are split in the fiber axis direction. It means 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. Reference numeral 1 denotes a state in which fibril aggregates mainly composed of cellulose microfibrils are split in the fiber axis direction. (fibrillated state). FIG. 2 is an enlarged photograph showing a state in which regenerated cellulose fibers are fibrillated, and reference numeral 2 indicates cellulose microfibrils.

EXAMPLES The present invention will be specifically described below 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) Polymerization degree measurement method From the viscosity of a solution in which cellulose fibers are dissolved in a cuprammonium solution, the following formula:
ηsp/c=KmM
Standinger's viscosity represented by {wherein ηsp: specific viscosity, c: cellulose concentration (moles of basic molecules/100 ml), Km: constant (5×10 ⁻⁴ ), and M: molecular weight of cellulose} It was carried out by the so-called viscosity method, which is determined based on the law.

Several types of cellulose fiber samples with different degrees of polymerization were dissolved in a cuprammonium solution in a molecularly dispersed state, and their degrees of polymerization were measured with a Nakano viscous tube based on the above formula, and then constant with a Tappy viscous tube. Measure the viscosity of the above cellulose sample when it is dissolved in a cuprammonium solution of a certain concentration, determine the relationship between the viscosity and the degree of polymerization in advance, dissolve it in the copper ammonium solution of the above constant concentration with a tappy type viscosity tube, and measure the viscosity. Then, the degree of polymerization was determined from a previously obtained relational table between the viscosity and the degree of polymerization.

The method of measuring viscosity using a tappy type viscosity tube is as follows. The sample is left in a constant temperature/humidity chamber with a temperature of 20° C. and a humidity of 65% for 24 hours or longer to equilibrate the moisture content. 0.1 g of the sample is weighed and collected. A wedge and a sample are placed in a tappy-type viscosity tube, and then a cuprammonium solution (composition: ammonia: 205 g/L, copper (I) hydroxide: 11.0 g/L, sucrose: 10 g/L) is sucked into the viscosity tube. Make a 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. Remove the viscosity tube from the rotating device and immerse it in a constant temperature water bath at 20°C for 5 minutes. Remove the plug at the bottom of the viscosity tube and insert the viscosity tube into the jacket set in the constant temperature water bath. Open the stopcock on the top of the viscometer and measure the time for the solution to flow down between the marked lines A and B of the viscometer. Formula below:
V=d/C(t-K/t)
{Wherein, V: absolute viscosity (cP), d: specific gravity of solution (g/cm ³ ), C: constant of tappy viscosity tube, t: flow-down time between marked lines A and B (seconds), and K: The flow energy constant of the tappy viscosity tube. } to determine the absolute viscosity (V). Then, the degree of polymerization was determined by comparing the determined absolute viscosity value with the above-described relationship table between the viscosity and the degree of polymerization.

(2) Dry Tensile Strength Test Method The sample was allowed to stand in a constant temperature and humidity chamber at a temperature of 20° C. and a humidity of 65% for 24 hours or longer to balance the moisture content. Using a Tensilon universal material testing machine RTC series (manufactured by A&D Co., Ltd.), the sample was pulled at a sample length (thread 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. 2 g of laundry detergent is added and dissolved in 1 L of water adjusted to a liquid temperature of 40° C. to obtain a washing liquid. A sample yarn and a load cloth are put into this washing liquid so that the bath ratio is 1:30, and the operation is started. After washing for 5 minutes, dehydrate, then rinse with normal temperature water at the same bath ratio for 2 minutes to dehydrate, rinse again with normal temperature water at the same bath ratio for 2 minutes, dehydrate, and wash once. do. The drying method was tumbler drying at 80°C for 20 minutes.

(4) Degree of fibrillation A sample is set in a microscope VHX-6000 (manufactured by Keyence Corporation), and the magnification of the lens VH-Z20 (manufactured by Keyence Corporation) is set to 200 times, while adjusting the conditions of brightness and sensitivity. , the sample is irradiated in parallel with light that causes the fibril portion to become a white point, and the sample is photographed. Next, the ratio of the area of the white spots to the photographed area was calculated, and the degree of fibrillation was evaluated based on the following three-level evaluation criteria.
○ (fibrillated): white point area ratio of 10% or more △ (insufficient fibrillation): white point area ratio of 5% or more and less than 10% × (not fibrillated): white point less than 5% of the area of

(5) Change in degree of fibrillation due to washing For the samples before and after washing, each sample was set in a microscope VHX-6000 (manufactured by Keyence), and the magnification of the lens VH-Z20 (manufactured by Keyence) was 200 times. In this state, while adjusting the brightness and sensitivity conditions, the sample is irradiated in parallel with light so that the fibril portion becomes a white point, and the sample is photographed. Then, the ratio of the white point area to the photographed area was calculated for the samples before and after washing, using the following formula:
X=AW-BW
{Wherein, X: change in degree of fibrillation due to washing (%), AW: ratio of area of white spots in sample after washing (%), and BW: ratio of area of white spots in sample before washing ( %). } 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-stage evaluation criteria.
○ (no change in fibrillation): amount of change is -10% or more and less than +10% × (change in fibrillation): amount of change is less than -10% or +10% or more

(6) Texture The texture of the sample before washing was evaluated based on the following 3-level evaluation criteria by a sensory test of touch by repeated gripping operations. Those with a result of 〇 or △ were evaluated:
○: Excellent in softness and resilience △: Slightly lacking in softness or resilience ×: Inferior in softness or resilience

[Example 1]
A cuprammonium rayon 84 dtex/45 filament having a degree of polymerization of 580 and a dry tensile strength of 2.3 cN/dtex was prepared. This raw thread was subjected to a modification treatment with a cheese dyeing machine using 76% formic acid at 1.0 g/L at 130° C. for 20 minutes to obtain a modified cuprammonium rayon with a degree of polymerization of 200. Using the modified cuprammonium rayon raw yarns as warps and wefts, a 2/1 twill fabric was woven with a warp density of 144/2.54 cm and a weft density of 100/2.54 cm. The resulting green fabric was scouring, relaxed and fibrillated with a nonionic surfactant of 1 g/L at 80°C for 20 minutes in a jet dyeing machine, and then again at a dyeing temperature of 60°C for 60 minutes in a jet dyeing machine. Dyeing of cupra ammonium rayon was performed, followed by soaping 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 a pick-up rate of 80%, dried at 150 ° C. for 1 minute, and dried at 80 ° C. for 30 minutes with an air tumbler at a speed of 700 m / min. A texture release treatment was carried out and a final set was carried out at 130° C. for 1 minute to obtain a dyed fabric with a warp density of 153/2.54 cm and a weft density of 104/2.54 cm. The degree of polymerization of the cupra-ammonium rayon 84 dtex/45 filament of the warp yarn taken out from the woven fabric was 200.

[Example 2]
Cupra ammonium rayon 84 dtex/45 filaments with a polymerization degree of 580 and a dry tensile strength of 2.3 cN/dtex are used for the warp and weft, with a warp density of 144/2.54 cm and a weft density of 100/2.54 cm. A 2/1 weave twill fabric was woven. The obtained green fabric was subjected to modification treatment and fibrillation treatment using 76% formic acid at 1.0 g / L at 130 ° C. for 20 minutes in a jet dyeing machine to make the degree of polymerization 200, and then jet dyeing again. Dyeing of cupra-ammonium rayon was carried out at a dyeing temperature of 60°C for 60 minutes, 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 softener, printed with a pick-up rate of 80%, dried at 150 ° C. for 1 minute, and dried at 80 ° C. for 30 minutes with an air tumbler at a speed of 700 m / min. A texture release treatment was carried out and a final set was carried out at 130° C. for 1 minute to obtain a dyed fabric with a warp density of 153/2.54 cm and a weft density of 104/2.54 cm. The degree of polymerization of the cupra-ammonium rayon 84 dtex/45 filament of the warp yarn taken out from the woven fabric was 200.

[Example 3]
An organic solvent method cellulose fiber 89 dtex/30 filaments having a degree of polymerization of 490 and a dry tensile strength of 3.5 cN/dtex was prepared. This raw yarn was subjected to a modification treatment using a cheese dyeing machine using 76% formic acid at 1.0 g/L at 130° C. for 20 minutes to obtain a modified organic solvent method cellulose fiber with a degree of polymerization of 220. Using the obtained modified organic solvent method cellulose fibers as warp and weft, a plain fabric having a warp density of 105/2.54 cm and a weft density of 89/2.54 cm was woven. The resulting green fabric is scouring, relaxed and fibrillated with a nonionic surfactant of 1 g/L at 80°C for 20 minutes in a jet dyeing machine, and then subjected to organic dyeing at a dyeing temperature of 60°C for 60 minutes in a jet dyeing machine. Dyeing of solvent-processed cellulose fibers was carried out followed by soaping 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 a pick-up rate of 80%, dried at 150 ° C. for 1 minute, and dried at 80 ° C. for 30 minutes with an air tumbler at a speed of 700 m / min. A texture release treatment was carried out, and a final set was carried out at 130° C. for 1 minute to obtain a dyed fabric with a warp density of 109/2.54 cm and a weft density of 92/2.54 cm. The degree of polymerization of the organic solvent method cellulose fiber 89 dtex/30 filament of the warp taken out from the fabric was 220.

[Example 4]
Organic solvent method cellulose fiber 89 dtex/30 filaments having a polymerization degree of 490 and a dry tensile strength of 3.5 cN/dtex were used for the warp and weft, and the warp density was 105/2.54 cm and the weft density was 89/2. A plain weave fabric of 54 cm was woven. The resulting green fabric was subjected to modification treatment and fibrillation treatment using 76% formic acid at 1.0 g / L at 130 ° C. for 20 minutes in a jet dyeing machine to make the degree of polymerization 220, and then jet dyeing again. The organic solvent method cellulose fibers were dyed 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 softener, printed with a pick-up rate of 80%, dried at 150 ° C. for 1 minute, and dried at 80 ° C. for 30 minutes with an air tumbler at a speed of 700 m / min. A texture release treatment was carried out, and a final set was carried out at 130° C. for 1 minute to obtain a dyed fabric with a warp density of 109/2.54 cm and a weft density of 92/2.54 cm. The degree of polymerization of the organic solvent method cellulose fiber 89 dtex/30 filament of the warp taken out from the fabric was 220.

[Comparative Example 1]
Cupra ammonium rayon 84 dtex/45 filaments with a polymerization degree of 580 and a dry tensile strength of 2.3 cN/dtex are used for the warp and weft, with a warp density of 144/2.54 cm and a weft density of 100/2.54 cm. A 2/1 weave twill fabric was woven. The resulting green fabric was dyed and finished in the same manner as in Example 2 except that the modification treatment and fibrillation treatment were not performed. of dyed fabric was obtained. The polymerization degree of the warp cuprammonium rayon 84 dtex/45 filament taken out from the woven fabric was 580.

[Comparative Example 2]
Organic solvent method cellulose fiber 89 dtex/30 filaments having a degree of polymerization of 490 and a tensile strength of 3.5 cN/dtex when dry is used for the warp and weft, and the warp density is 109/2.54 cm and the weft density is 92/2.54 cm. A plain weave fabric was woven. The obtained green fabric was dyed and finished in the same manner as in Example 4 except that the modification treatment and fibrillation treatment were not performed, and the warp density was 109/2.54 cm, and the weft density was 92/2.54 cm. of dyed fabric was obtained. The polymerization degree of the organic solvent method cellulose fiber 89 dtex/30 filament of the warp taken out from the woven fabric was 490.

[Comparative Example 3]
Cupra ammonium rayon 84 dtex/45 filaments with a polymerization degree of 580 and a dry tensile strength of 2.3 cN/dtex are used for the warp and weft, with a warp density of 144/2.54 cm and a weft density of 100/2.54 cm. A 2/1 weave twill fabric was woven. The resulting green fabric was fibrillated with 40 g/L sodium hydroxide at 80° C. for 120 minutes with a jet dyeing machine, and again with a jet dyeing machine at a dyeing temperature of 60° C. for 60 minutes to make cupra ammonium rayon. and then soaping 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 a pick-up rate of 80%, dried at 150 ° C. for 1 minute, and dried at 80 ° C. for 30 minutes with an air tumbler at a speed of 700 m / min. A texture release treatment was carried out and a final set was carried out at 130° C. for 1 minute to obtain a dyed fabric with a warp density of 153/2.54 cm and a weft density of 104/2.54 cm. The degree of polymerization of the cupra-ammonium rayon 84 dtex/45 filaments of the warp taken out from the fabric was 440.

[Comparative Example 4]
Cupra ammonium rayon 84 dtex/45 filaments with a polymerization degree of 580 and a dry tensile strength of 2.3 cN/dtex are used for the warp and weft, with a warp density of 144/2.54 cm and a weft density of 100/2.54 cm. A 2/1 weave twill fabric was woven. The resulting green fabric was fibrillated with 50 g/L of 75% phosphoric acid in a jet dyeing machine at 100°C for 60 minutes, and again with a jet dyeing machine at a dyeing temperature of 60°C for 60 minutes with cupra ammonium. Dyeing of rayon was performed, 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 softener, printed with a pick-up rate of 80%, dried at 150 ° C. for 1 minute, and dried at 80 ° C. for 30 minutes with an air tumbler at a speed of 700 m / min. A texture release treatment was carried out and a final set was carried out at 130° C. for 1 minute to obtain a dyed fabric with a warp density of 153/2.54 cm and a weft density of 104/2.54 cm. The degree of polymerization of the cupra-ammonium rayon 84 dtex/45 filaments of the warp taken out from the woven fabric was 400.

[Comparative Example 5]
Cupra ammonium rayon 84 dtex/45 filaments with a polymerization degree of 580 and a dry tensile strength of 2.3 cN/dtex are used for the warp and weft, with a warp density of 144/2.54 cm and a weft density of 100/2.54 cm. A 2/1 weave twill fabric was woven. The resulting green fabric was fibrillated with a 35% hydrogen peroxide aqueous solution of 30 g/L at 100°C for 60 minutes using a jet dyeing machine, and then again with a jet dyeing machine at a dyeing temperature of 60°C for 60 minutes. Dyeing of cupra ammonium rayon was performed, followed by soaping 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 a pick-up rate of 80%, dried at 150 ° C. for 1 minute, and dried at 80 ° C. for 30 minutes with an air tumbler at a speed of 700 m / min. A texture release treatment was carried out and a final set was carried out at 130° C. for 1 minute to obtain a dyed fabric with a warp density of 153/2.54 cm and a weft density of 104/2.54 cm. The warp cuprammonium rayon 84 dtex/45 filament taken out from the fabric had a degree of polymerization of 180.

[Comparative Example 6]
Cupra ammonium rayon 84 dtex/45 filaments with a polymerization degree of 580 and a dry tensile strength of 2.3 cN/dtex are used for the warp and weft, with a warp density of 144/2.54 cm and a weft density of 100/2.54 cm. A 2/1 weave twill fabric was woven.
The resulting gray fabric was fibrillated with acetic acid at 6.4 g/L at 130° C. for 45 minutes with an air-stream dyeing machine, and then cupra ammonium was added at a dyeing temperature of 60° C. for 360 minutes with an air-stream dyeing machine. Dyeing of rayon was performed, and then soaping was performed at 80° C. for 10 minutes. After dyeing and drying, immerse in an aqueous solution containing 1% by weight of silicone softener, pick up 80% liquid, dry at 150 ° C. for 1 minute, and use an air tumbler at 100 ° C. for 30 minutes at a speed of 900 m / min. A texture release treatment was carried out and a final set was carried out at 130° C. for 1 minute to obtain a dyed fabric with a warp density of 153/2.54 cm and a weft density of 104/2.54 cm. The warp cuprammonium rayon 84 dtex/45 filament taken out from the fabric had a degree of polymerization of 190.

For the woven fabrics obtained in Examples 1 to 4 and Comparative Examples 1 to 6, the sample fabrics that were washed 10 times by the above washing test method, and the sample fabrics that were not washed, the degree of fibrillation and washing Evaluation of change in degree of fibrillation and texture was carried out. In addition, cuprammonium rayon 84 dtex / 45 filaments and organic solvent method cellulose fibers 89 dtex / 30 filaments subjected to warp modification treatment and fibrillation treatment from the fabric samples of Examples 1 to 4 were added to the fabric samples of Comparative Examples 1 to 6. A cuprammonium rayon 84 dtex/45 filament and an organic solvent method cellulose fiber 89 dtex/30 filament of warp yarns that have not been modified or have been fibrillated with different fibrillation treatments were taken out from the test, and the tensile strength of the warp yarns when dried was measured. 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 6, and Table 2 below shows the evaluation results.

The fabrics using the modified cellulose fibers of Examples 1 to 4 had good texture with softness and resilience without change in fibril feeling due to washing, and also had a tensile strength of 1.0 cN/dtex. is found to exceed That is, Examples 1 to 4 have a characteristic surface feeling, softness, and a feeling of resilience after washing, and are excellent in durability of the surface feeling and feeling after washing.
On the contrary, the fabrics of Comparative Examples 1 to 6 have a tensile strength of 1.0 cN / dtex or less, or fibrils are removed at the stage before washing, or the degree of polymerization exceeds 250 and 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 texture and texture due to washing is large, or the strength as a fabric is not maintained, and holes are formed due to abrasion during wearing or washing, or before washing. Since the fibrils are removed at the stage of (1), it is not suitable as a fiber product having fibrils that requires good feel.

According to the present invention, it has a characteristic surface feeling, softness, and resilience texture, is easily fibrillated by friction and soft cloth treatment in a wet state, and maintains its surface texture and texture even after washing with water. INDUSTRIAL APPLICABILITY The present invention has industrial applicability because it is possible to provide regenerated cellulose fibers with excellent properties and high-class feeling, and fabrics using the fibers.

1 State in which fibril aggregates mainly composed of cellulose microfibrils are split in the fiber axis direction (fibrillated state)
2 Cellulose microfibrils

Claims (4)

A regenerated cellulose fiber having a fibrillated surface, having a polymerization degree of 100 to 250 and a dry tensile strength of more than 1.0 cN/dtex and not more than 3.0 cN/dtex. 2. The regenerated cellulose fiber according to claim 1, wherein the regenerated cellulose fiber is an organic solvent method cellulose fiber. A fabric comprising the regenerated cellulose fiber according to claim 1 or 2 as constituent yarn. Regenerated cellulose fibers in the form of yarn or fabric are subjected to modification treatment in an acid solution at a temperature of 110 ° C. to 150 ° C. for 10 minutes to 30 minutes and at a pH of 2.6 to 3.4. A method for producing the regenerated cellulose fiber according to claim 1 or 2 or the fabric according to claim 3.

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