CN114929962B - Fibrillated regenerated cellulose fiber and fabric made of the same - Google Patents
Fibrillated regenerated cellulose fiber and fabric made of the same Download PDFInfo
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- CN114929962B CN114929962B CN202080091831.8A CN202080091831A CN114929962B CN 114929962 B CN114929962 B CN 114929962B CN 202080091831 A CN202080091831 A CN 202080091831A CN 114929962 B CN114929962 B CN 114929962B
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
- D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
- D01F2/04—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts from cuprammonium solutions
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/208—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based
- D03D15/225—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based artificial, e.g. viscose
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/573—Tensile strength
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/20—Cellulose-derived artificial fibres
- D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
提供具有特征性的表面感、柔软性和有反弹感的手感，通过湿润状态下的摩擦/揉布处理而原纤维化，并且对于水洗涤的表面感、手感的持续性优异的具有高级感的原纤维化的再生纤维素纤维、以及使用了该纤维的布帛。一种表面原纤维化的再生纤维素纤维，其聚合度为100～250、并且干燥时的拉伸强度超过1.0cN/dtex且为3.0cN/dtex以下。一种布帛，其含有该再生纤维素纤维作为构成丝。一种前述表面原纤维化的再生纤维素纤维和含有该再生纤维素纤维作为构成丝的布帛的制造方法，其包括对再生纤维素纤维以丝条或布帛的形态在酸溶液中、温度110℃～150℃、时间10分钟～30分钟、pH 2.6～3.4的条件下进行改质处理的工序。
A high-quality fibrillated regenerated cellulose fiber having a characteristic surface feel, softness, and a resilient feel, which is fibrillated by rubbing/kneading in a wet state, and has excellent durability of surface feel and feel after washing with water, and a fabric using the fiber. A surface fibrillated regenerated cellulose fiber having a degree of polymerization of 100 to 250 and a tensile strength of more than 1.0 cN/dtex and less than 3.0 cN/dtex when dried. A fabric containing the regenerated cellulose fiber as a constituent filament. A method for producing the aforementioned surface fibrillated regenerated cellulose fiber and a fabric containing the regenerated cellulose fiber as a constituent filament, comprising the step of modifying the regenerated cellulose fiber in the form of a filament or a fabric in an acid solution at 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.
Description
Technical Field
The present invention relates to fibrillated regenerated cellulose fibers having a characteristic surface feel, softness and a rebound feel, which are fibrillated by rubbing/kneading in a wet state, and which are excellent in surface feel and durability of the hand feel to water washing, and to fabrics containing the same as constituent filaments.
Background
The regenerated cellulose fiber exists copper ammonium rayon, organic solvent cellulose fiber and the like, and the cellulose fiber has the following characteristics: the cellulose microfibrils are formed of a fibril aggregate mainly composed of cellulose microfibrils, and when the cellulose microfibrils are rubbed and kneaded in a wet state, the cellulose is fibrillated in the fiber axis direction, and fibrillated.
In a clothing produced using regenerated cellulose fibers, there are many products that are produced by fibrillating regenerated cellulose fibers constituting the clothing using such characteristics because the clothing exhibits a characteristic surface feel, softness, and a rebound feel, but when the fibrillated clothing is repeatedly washed with water, the fibrils fall off, and there is a problem that the surface feel and the feel are impaired. In addition, although there is a prior art document on fibrillation of regenerated cellulose fibers, there is no prior art document providing a specific solution to this problem.
For example, as a processing method for fibrillation, patent document 1 below discloses a method of utilizing a fluffing treatment and an impact at the time of dyeing by a flow dyeing machine. However, the amount of fibrils appearing is not fixed depending on dyeing conditions such as dyeing time, bath ratio, cloth speed, and concentration of alkali used, and therefore, there is a disadvantage that the same quality of commodity cannot be repeatedly provided, and the degree of polymerization of regenerated cellulose fibers is regulated to 400 or more, and no mention is made of the shedding of fibrils due to water washing.
The following patent document 2 discloses fibrillation by an aqueous alkali solution. However, the degree of polymerization of the regenerated cellulose fibers is set to 300 or more, and the treatment method is a treatment in an aqueous alkali solution, and the regenerated cellulose fibers are structurally easily fibrillated only in the aqueous alkali solution, so that fibrillation is difficult in a weakly alkaline water washing, and the shedding of fibrils due to the water washing is not mentioned.
Patent document 3 below discloses a method of using an aqueous acid solution or an aqueous oxidizing agent solution, although the polymerization degree of regenerated cellulose fibers is not described. The conditions of the treatment method described in patent document 3 are, in comparison with the conditions disclosed in the present specification, that the treatment is performed for a long period of time in a high-concentration acid solution at a high temperature under normal pressure in order to suppress the decrease in strength, but there is no description of the rate of decrease in strength due to such a treatment method, and there is a description of the decrease in strength when the treatment is performed under a high pressure, which is not the same as the treatment conditions disclosed in the present specification.
Patent document 4 below discloses a method using an aqueous acid solution, although the polymerization degree of regenerated cellulose fibers is not described. Patent document 4 describes a treatment with an aqueous acid solution for 30 to 80 minutes, which aims at reducing the strength, and a high-speed tumbling treatment in a dry state, in order to remove long fibrils. However, the lyocell-containing fabric disclosed in patent document 4 removes long fibrils which provide a "hairy effect (HAIRY EFFECT)" as a characteristic surface feel disclosed in the present specification to the fabric surface, and short fibrils which are present on the fabric surface, and patent document 4 describes a surface finish which is characterized by "clean" substantially free of "HAIRY EFFECT" unlike the fibrillated regenerated cellulose fibers disclosed in the present specification. Patent document 4 does not describe the strength reduction rate of the cloth due to the treatment method for removing long fibrils, and does not mention the shedding of fibrils due to water washing.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 08-113846
Patent document 2: japanese patent laid-open No. H06-166956
Patent document 3: japanese patent laid-open No. 11-315474
Patent document 4: british patent No. 2399094A
Disclosure of Invention
Problems to be solved by the invention
In view of the above-described conventional techniques, an object of the present invention is to provide fibrillated regenerated cellulose fibers having a characteristic surface feel, softness and a rebound feel, which are fibrillated by rubbing/kneading treatment in a wet state, and which are excellent in surface feel and durability of the feel in water washing, and a fabric using the same.
Solution for solving the problem
The present inventors have intensively studied to solve the above-mentioned problems, and as a result, have found that, as compared with the case of modifying the regenerated cellulose fiber so that the fibrils do not fall off, it is effective to modify the regenerated cellulose fiber so that the fibrils do not fall off during washing, and as a result, have unexpectedly found that, when the polymerization degree of the regenerated cellulose fiber is controlled to 100 to 250, the fibrils easily appear only by the weak kneading effect of washing, and the feel of the regenerated cellulose fiber exhibits softness and rebound feeling with a light feel, based on the above-mentioned findings, and have completed the present invention.
Namely, the present invention is as follows.
[1] A surface fibrillated regenerated cellulose fiber having a degree of polymerization of 100 to 250 and a tensile strength at drying exceeding 1.0cN/dtex and not more than 3.0 cN/dtex.
[2] The regenerated cellulose fiber according to the above [1], wherein the regenerated cellulose fiber is an organic solvent-based cellulose fiber.
[3] A fabric comprising the regenerated cellulose fiber according to [1] or [2] as a constituent yarn.
[4] The method for producing a regenerated cellulose fiber according to [1] or [2] or the fabric according to [3], which comprises a step of modifying the regenerated cellulose fiber in the form of a yarn or fabric in an acid solution at a temperature of 110 to 150 ℃ for 10 to 30 minutes and at a pH of 2.6 to 3.4.
ADVANTAGEOUS EFFECTS OF INVENTION
The fibrillated regenerated cellulose fiber of the present invention is a fiber having a characteristic surface feel, softness, and a feel with a rebound feel, fibrillated by rubbing/kneading treatment in a wet state, and having a high-quality feel excellent in durability of the surface feel and feel in washing.
Drawings
Fig. 1 is a photograph showing the surface of a fabric in a state in which regenerated cellulose fibers constituting filaments are fibrillated.
Fig. 2 is a photograph showing the state of regenerated cellulose fiber fibrillation in an enlarged manner.
Detailed Description
Embodiments of the present invention are described in detail below.
An embodiment 1 of the present invention is a surface fibrillated regenerated cellulose fiber having a degree of polymerization of 100 to 250 and a tensile strength at drying exceeding 1.0cN/dtex and not more than 3.0 cN/dtex.
The regenerated cellulose fibers are regenerated cellulose fibers obtained by dissolving and spinning a cellulose raw material such as cuprammonium rayon or organic solvent-based cellulose fibers, and are preferably cuprammonium rayon or organic solvent-based cellulose fibers, and more preferably organic solvent-based cellulose fibers.
The form of the filament yarn of the regenerated cellulose fiber may be any of short fibers and long fibers, and is preferably a multifilament of long fibers. The fineness of the filaments is not particularly limited, and may be preferably 0.5 to 5.0dtex. The total fineness is not particularly limited, and is preferably 22 to 330dtex, and the count is not particularly limited, but is preferably 5 to 100 cotton counts. The cross-sectional shape of the monofilament is also not particularly limited. The number of turns is not particularly limited, and the number of turns may be preferably 2000 or less times by adding a twist. From the viewpoint of the hand feeling, no twist is preferable.
The present embodiment is not particularly limited as to the compounding with other materials because it is not affected by other materials, but is not preferable as other materials to be compounded, that is, because acrylic acid, diacetate, wool are easily reduced in strength, cured touch, devitrified, and the like due to the treatment under high pressure as a processing method.
The use ratio of the regenerated cellulose fiber in the fabric containing the woven fabric or the nonwoven fabric is not particularly limited, but is preferably 10% by weight or more, more preferably 20% by weight or more, and still more preferably 30% by weight or more based on the total weight of the fabric in order to satisfactorily exert the desired effect. When the use ratio is 10% by weight or less, fibrillation is found, but softness and rebound feeling are hardly obtained. The method of compounding the filaments may be any of doubling, interlacing, spun yarn blending, covering, cotton blending, drawing blending, and spinning and twisting.
The fibrillated regenerated cellulose fibers of the present embodiment have a degree of polymerization of 100 to 250, preferably 150 to 250, more preferably 200 to 250. If the polymerization degree is less than 100, the tensile breaking strength at the time of drying is 1.0cN/dtex or less, and the fiber properties necessary for post-processing until formation of a fabric and use as a clothing are not achieved. On the other hand, if the polymerization degree is higher than 250, the re-occurrence of fibrils by water washing cannot be obtained, which is not preferable. The polymerization degree refers to a value measured by a viscosity method using a cuprammonium solution.
The fabric may be any of a fabric, a warp knitting, a circular knitting, a weft knitting, and a nonwoven fabric, and is preferably a fabric, a warp knitting, a circular knitting, a weft knitting, and more preferably a fabric or a circular knitting. The structure and density of the fabric are not particularly limited. The compounding method for compounding with other raw materials may be any of interlacing, stitch bonding, use of composite yarn, weft insertion in warp knitting, and the like.
In the present embodiment, the method of the modification treatment for adjusting the polymerization degree of the fibrillated regenerated cellulose fibers to 100 to 250 is not particularly limited. However, the regenerated cellulose fiber having a polymerization degree of 250 or more and a tensile strength of 2.0cN/dtex or more at the time of drying is treated in an acid solution to adjust the polymerization degree to 100 to 250 and the tensile strength at the time of drying to more than 1.0cN/dtex and 3.0cN/dtex or less, and thus the use thereof is particularly preferred because the fiber is excellent in terms of the fiber properties and the ease of adjustment of the polymerization degree. The type of the 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, and the like, and is preferably an acid less corrosive to metals, more preferably formic acid, citric acid, and malic acid. The treatment temperature is preferably 110 to 150 ℃, more preferably 120 to 150 ℃, and even more preferably 130 to 140 ℃ in order to modify the polymerization degree to the target and the tensile strength to the target. When the temperature is lower than 110 ℃, a long treatment is required for the modification, and even if the degree of polymerization and tensile strength to be modified are significantly reduced, it is not preferable. In addition, when the treatment is performed at a temperature lower than 110 ℃ for a short period of time, it is necessary to reduce the pH, and when the treatment is performed at a low pH for a short period of time, local reduction in polymerization degree and strength occurs, and uniform modification is difficult, and variation in quality occurs in each modification treatment, which is not preferable. On the other hand, when 150 ℃ or higher, it is not preferable because it is difficult to control the temperature and it is difficult to uniformly modify the material. The treatment pH and the treatment time are adjusted according to the regenerated cellulose fibers to be used, and the treatment pH is preferably 2.6 to 3.4, more preferably 2.8 to 3.2, and the treatment time is preferably 10 minutes to 30 minutes, more preferably 12 minutes to 28 minutes, and further preferably 15 minutes to 25 minutes. For example, when a regenerated cellulose fiber having a polymerization degree of about 450 to 600 and a tensile strength of 2.0cN/dtex or more at the time of drying is treated with formic acid, the polymerization degree can be modified to 100 to 250 by treating the regenerated cellulose fiber with an acid bath having a pH of 2.8 and a formic acid concentration of 1.0g/L at 76% at 130℃for 20 minutes, and the tensile strength at the time of drying can be maintained at more than 1.0cN/dtex and 3.0cN/dtex or less. In order to reduce the polymerization degree to the target polymerization degree in a short time and to modify the tensile strength at the time of drying to more than 1.0cN/dtex and 3.0cN/dtex or less, a short-time modification treatment with a low concentration of acid is required, and a high-temperature and high-pressure treatment at 110℃or higher is required.
The form of the modifying treatment is not particularly limited, but is preferably a yarn form, a fabric form, or more preferably a fabric form. The yarn form and the fabric form are not particularly limited as to the equipment used in the processing, but a cone dyeing machine and a hank dyeing machine are preferable as the yarn form, and a liquid flow dyeing machine, an air flow dyeing machine, a warp dyeing machine, a jig dyeing machine, a blade dyeing machine, a drum dyeing machine, a gasket dyeing machine (WASHER DYER), a winch rope dyeing machine, and more preferable liquid flow dyeing machine and an air flow dyeing machine as the fabric form.
In order to generate fibrils after the modification treatment, the fibrillation treatment in water is required, and thus, the fibrillation treatment is required to be performed simultaneously with the modification treatment or after the modification treatment. The form of the fibrillation treatment is not particularly limited, but is preferably a fabric form. The equipment used in the processing is not particularly limited, but is preferably a liquid flow dyeing machine, a gas flow dyeing machine, a paddle dyeing machine, a drum dyeing machine, a gasket dyeing machine, a winch rope dyeing machine, more preferably a liquid flow dyeing machine, a gas flow dyeing machine. The fibrillation treatment in water is not particularly limited, and is preferably, for example, a liquid flow dyeing machine, an air flow dyeing machine, or a winch rope dyeing machine as equipment, a treatment time at a temperature of 10 to 130 ℃ for a fabric speed of 100 m/min or more and 20 minutes or more, or a fibrillation treatment at a temperature of 10 to 130 ℃ for a treatment time of 20 minutes or more as equipment. Further, since it is necessary that the fibrils are not removed after the occurrence of the fibrils, it is preferable that the handling treatment in a dry state is not performed after the occurrence of the fibrils, or the handling treatment in a dry state is performed, for example, the handling treatment in a condition in which the speed of the fabric is 800 m/min or less and 60 min or less using an air-jet dyeing machine or an air-jet drum dryer, or the handling treatment in a condition in which 60 min or less using a batch-type drum dryer is used as the handling treatment in the apparatus.
The regenerated cellulose fiber according to the present embodiment has a tensile strength at the time of drying of more than 1.0cN/dtex and 3.0cN/dtex or less, preferably 1.3cN/dtex or more and 2.5cN/dtex or less, more preferably 1.5cN/dtex or more and 2.0cN/dtex or less. If the tensile strength at the time of drying is 1.0cN/dtex or less, the fabric is hardly obtained due to damage or the like in various steps until the fabric is produced, and the rebound feeling is impaired, and if the tensile strength exceeds 3.0cN/dtex, the softness is impaired.
The term "fibrillated" in the fibrillated regenerated cellulose fibers of the present embodiment refers to a state in which a fibril aggregate mainly composed of cellulose microfibrils constituting the surface of the regenerated cellulose fibers is cut in the fiber axis direction. Fig. 1 is a photograph showing the surface of a fabric in a fibrillated state of regenerated cellulose fibers constituting filaments, and reference numeral 1 indicates a state in which a fibril aggregate of cellulose microfibrils as a main body is fibrillated in the fiber axis direction (fibrillated state). Fig. 2 is a photograph showing an enlarged state of regenerated cellulose fiber fibrillation, and reference numeral 2 denotes cellulose microfibrils.
Examples
The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The various properties of each yarn or fabric in the examples were evaluated by the following methods.
(1) Polymerization degree measurement method
The viscosity of a solution obtained by dissolving cellulose fibers in a cuprammonium solution is based on the following formula:
ηsp/c＝KmM
{ formula, ηsp: specific viscosity, c: cellulose concentration (moles of basic molecule per 100 ml), km: constant (5×10 -4), and M: the viscosity method is performed by determining the viscosity of STANDINGER shown in the molecular weight of cellulose.
The polymerization degree is determined from a table of the relationship between the viscosity and the polymerization degree obtained in advance by measuring the viscosity of a solution of copper ammonia at a predetermined concentration for the cellulose sample by using a TAPPI type viscosity tube, and by measuring the viscosity of a solution of copper ammonia at a predetermined concentration by using a TAPPI type viscosity tube.
The method for measuring the viscosity using TAPPI-type viscosity tube is as follows. The sample was placed in a constant temperature humidity chamber at 20℃and 65% humidity for 24 hours or more to equilibrate the water content. 0.1g of the sample was weighed and collected. A wedge and sample were added to the TAPPI-type viscosity tube, and then a cuprammonium solution (composition: ammonia: 205g/L, copper (I) hydroxide: 11.0g/L, sucrose: 10 g/L) was sucked into the viscosity tube and capped. The viscosity tube was mounted on a rotating device and rotated at 3RPM for 30 minutes to dissolve the sample. The viscosity tube was removed from the rotary apparatus and immersed in a constant temperature water bath at 20℃for 5 minutes. The plug at the lower part of the viscosity tube was removed, and the viscosity tube was inserted into a jacket in a state of being attached to a constant temperature water tank. The valve of the stopper at the upper part of the viscosity tube was opened, and the time for the solution to flow down between the marks A, B of the viscometer was measured. The following calculation formula is used:
V＝d/C(t-K/t)
{ formula, V: absolute viscosity (cP), d: specific gravity of solution (g/cm 3), C: constant of TAPPI viscosity tube, t: the flow down time (seconds) between markings a-B, and K: the absolute viscosity (V) was determined from the flow energy constant of TAPPI viscosity tube. Next, the polymerization degree is determined by comparing the absolute viscosity value obtained with the aforementioned viscosity-polymerization degree relationship table.
(2) Tensile Strength test method at drying
The sample was placed in a constant temperature humidity chamber at 20℃and 65% humidity for 24 hours or more to equilibrate the water content. The strength at break was measured by stretching the specimen with a specimen length (filament length) of 200mm and a stretching speed of 200 mm/min using TENSILON universal tester RTC series (manufactured by A & D Company, limited).
(3) Washing test method
According to JIS L0217-103 method. A detergent for dissolving clothes was added to 1L of water having a liquid temperature of 40℃at a rate of 2g, and the mixture was used as a washing liquid. The sample yarn and the load cloth were put into the washing solution so that the bath ratio was 1:30, and the operation was started. After washing for 5 minutes, dehydration was performed, followed by washing with the same water bath ratio for 2 minutes, dehydration was performed, washing with the same water bath ratio for 2 minutes was performed again, and after dehydration, 1 washing was completed. The drying process is carried out for 20 minutes at 80 ℃.
(4) Degree of fibrillation
A sample was mounted on a microscope VHX-6000 (manufactured by KEYENCE CORPORATION), and the sample was photographed while adjusting conditions of brightness and sensitivity in a state where the magnification of a lens VH-Z20 (manufactured by KEYENCE CORPORATION) was 200 times, while irradiating a portion of the sample in parallel with light such that the fibril became a white point. Then, the ratio of the area of the white point to the imaging area was calculated, and the degree of fibrillation was evaluated based on the following 3-level evaluation criteria.
O (fibrillation): the ratio of the area of the white point is more than 10 percent
Delta (insufficient fibrillation): the ratio of the area of the white point is more than 5% and less than 10%
X (no fibrillation): the ratio of the areas of the white points is less than 5%
(5) Variation of degree of fibrillation by washing
For the sample before and after washing, the sample was mounted on a microscope VHX-6000 (KEYENCE CORPORATION), and the sample was photographed while adjusting conditions of brightness and sensitivity in a state where magnification of a lens VH-Z20 (KEYENCE CORPORATION) was 200 times, while irradiating a portion of the sample with light such that a fibril became white point in parallel. Then, the ratio of the area of the white point to the photographed area was calculated for the sample before and after washing, by the following calculation formula:
X＝AW-BW
In the formula { X: change in degree of fibrillation (%) due to washing, AW: ratio (%) of white point area in the washed sample, and BW: the ratio (%) of the area of the white point in the sample before washing was determined 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 3-level evaluation criteria.
O (no change in fibrillation): the variation is more than-10% and less than +10%
X (change in fibrillation): the variation is less than-10% or more than +10%
(6) Hand feel
The hand feeling of the sample before washing was evaluated based on the following 3-level evaluation criteria by using a functional test of hand feeling by repeated grasping operation, and the evaluation result of the sample before washing was good or Δ for the sample after washing:
And (2) the following steps: excellent in softness and rebound feeling
Delta: slightly insufficient softness or rebound feeling
X: poor softness or rebound feeling
Example 1
An 84dtex/45 filament of cuprammonium rayon having a degree of polymerization of 580 and a tensile strength of 2.3cN/dtex when dried was prepared. The yarn was subjected to a modification treatment of 130℃for 20 minutes using 76% formic acid at 1.0g/L by a cone dyeing machine, and the polymerization degree was set to 200 to obtain a modified cuprammonium rayon. The modified cuprammonium rayon obtained was used for warp and weft, and a 2/1-weave twill fabric comprising 144 warp yarns/2.54 cm and 100 weft yarns/2.54 cm was woven. The obtained grey cloth was subjected to 80℃20 minutes of refining relaxation and fibrillation treatment with a nonionic surfactant 1g/L by a flow dyeing machine, and then subjected to dyeing of an artificial copper ammonium filament again by a flow dyeing machine at a dyeing temperature of 60℃for 60 minutes, followed by a 10 minutes soaping at 80 ℃. After dyeing and drying, the fabric was impregnated with an aqueous solution containing 1 wt% of a silicon-based softener, subjected to padding (Squeeze to 80% wet pick-up) at a padding ratio of 80%, dried at 150℃for 1 minute, subjected to a treatment for providing a hand feeling by an air drum at 80℃for 30 minutes at a speed of 700 m/min, and subjected to final setting at 130℃for 1 minute, to thereby obtain a dyed fabric having a warp density of 153 pieces/2.54 cm and a weft density of 104 pieces/2.54 cm. The warp yarn of the cuprammonium rayon taken out of the fabric had a degree of polymerization of 84dtex/45 filaments of 200.
Example 2
The warp yarn and the weft yarn are made of copper ammonium rayon yarn 84dtex/45 long yarn with the polymerization degree of 580 and the tensile strength of 2.3cN/dtex in drying, and a twill fabric with 2/1 structure, which is composed of 144 warp yarns/2.54 cm and 100 weft yarns/2.54 cm, is woven. The resultant grey cloth was subjected to a 130℃20-minute modification treatment and fibrillation treatment with a flow dyeing machine using 76% formic acid at 1.0g/L, and after setting the degree of polymerization to 200, was again subjected to dyeing with a flow dyeing machine at a dyeing temperature of 60℃for 60 minutes and then to a 10-minute soaping at 80 ℃. After dyeing and drying, the fabric was impregnated with an aqueous solution containing 1 wt% of a silicon-based softener, subjected to padding at a padding ratio of 80%, dried at 150℃for 1 minute, subjected to a treatment for providing a hand feeling by an air drum at 80℃for 30 minutes at a speed of 700 m/min, and finally subjected to setting at 130℃for 1 minute, to thereby obtain a dyed fabric having a warp density of 153 yarns/2.54 cm and a weft density of 104 yarns/2.54 cm. The warp yarn of the cuprammonium rayon taken out of the fabric had a degree of polymerization of 84dtex/45 filaments of 200.
Example 3
An organic solvent-based cellulose fiber 89dtex/30 filament having a degree of polymerization of 490 and a tensile strength of 3.5cN/dtex at the time of drying was prepared. The raw filaments were subjected to a modification treatment of 130℃for 20 minutes at 1.0g/L using 76% formic acid by a cone dyeing machine, and the degree of polymerization was set to 220, to obtain modified organic solvent-based cellulose fibers. The modified organic solvent cellulose fibers obtained were used for warp and weft yarns to weave a plain weave fabric having a warp density of 105 yarns/2.54 cm and a weft density of 89 yarns/2.54 cm. The obtained grey cloth was subjected to 80℃20 minutes of refining relaxation and fibrillation treatment with a nonionic surfactant 1g/L by a flow dyeing machine, and then subjected to dyeing of cellulose fibers by an organic solvent method at a dyeing temperature of 60℃for 60 minutes by a flow dyeing machine again, followed by 10 minutes of soaping at 80 ℃. After dyeing and drying, the fabric was impregnated with an aqueous solution containing 1 wt% of a silicon-based softener, subjected to padding at a padding ratio of 80%, dried at 150℃for 1 minute, subjected to a treatment for providing a hand feeling by an air drum at 80℃for 30 minutes at a speed of 700 m/min, and finally subjected to setting at 130℃for 1 minute, to thereby obtain a dyed fabric having a warp density of 109 yarns/2.54 cm and a weft density of 92 yarns/2.54 cm. The organic solvent-based cellulose fibers of the warp yarn taken out of the fabric had a degree of polymerization of 89dtex/30 filaments of 220.
Example 4
The warp yarn and weft yarn are woven into a plain weave fabric having a warp yarn density of 105 yarns/2.54 cm and a weft yarn density of 89 yarns/2.54 cm using organic solvent-process cellulose fibers 89dtex/30 filaments having a degree of polymerization of 490 and a tensile strength of 3.5cN/dtex at the time of drying. The obtained grey cloth was subjected to a modification treatment and fibrillation treatment at 130℃for 20 minutes using a flow dyeing machine at 1.0g/L with 76% formic acid, the polymerization degree was set to 220, and then, the dyed cellulose fiber was subjected to a dyeing treatment by an organic solvent method at 60℃for 60 minutes again using a flow dyeing machine, and then, was subjected to a soaping treatment at 80℃for 10 minutes. After dyeing and drying, the fabric was impregnated with an aqueous solution containing 1 wt% of a silicon-based softener, subjected to padding at a padding ratio of 80%, dried at 150℃for 1 minute, subjected to a treatment for providing a hand feeling by an air drum at 80℃for 30 minutes at a speed of 700 m/min, and finally subjected to setting at 130℃for 1 minute, to thereby obtain a dyed fabric having a warp density of 109 yarns/2.54 cm and a weft density of 92 yarns/2.54 cm. The organic solvent-based cellulose fibers of the warp yarn taken out of the fabric had a degree of polymerization of 89dtex/30 filaments of 220.
Comparative example 1
The warp yarn and the weft yarn are made of copper ammonium rayon yarn 84dtex/45 long yarn with the polymerization degree of 580 and the tensile strength of 2.3cN/dtex in drying, and a twill fabric with 2/1 structure, which is composed of 144 warp yarns/2.54 cm and 100 weft yarns/2.54 cm, is woven. Dyeing and finishing were performed in the same manner as in example 2 except that the obtained grey fabric was not subjected to the modifying treatment and the fibrillation treatment, to obtain a dyed fabric having a warp density of 153 yarns/2.54 cm and a weft density of 104 yarns/2.54 cm. The warp yarn of the cuprammonium rayon taken out of the fabric had a degree of polymerization of 84dtex/45 filaments of 580.
Comparative example 2
The warp yarn and weft yarn are woven into a plain weave fabric having a warp yarn density of 109 yarns/2.54 cm and a weft yarn density of 92 yarns/2.54 cm using organic solvent-process cellulose fibers 89dtex/30 filaments having a degree of polymerization of 490 and a tensile strength of 3.5cN/dtex at the time of drying. The same dyeing and finishing as in example 4 were carried out without modifying the resultant grey fabric and without fibrillation, to obtain a dyed fabric having a warp density of 109 yarns/2.54 cm and a weft density of 92 yarns/2.54 cm. The organic solvent-based cellulose fibers of the warp yarn taken out of the fabric had a degree of polymerization of 89dtex/30 filaments of 490.
Comparative example 3
The warp yarn and the weft yarn are made of copper ammonium rayon yarn 84dtex/45 long yarn with the polymerization degree of 580 and the tensile strength of 2.3cN/dtex in drying, and a twill fabric with 2/1 structure, which is composed of 144 warp yarns/2.54 cm and 100 weft yarns/2.54 cm, is woven. The obtained grey cloth was fibrillated by a liquid flow dyeing machine at 40g/L with sodium hydroxide for 120 minutes at 80℃and dyed with copper ammonium rayon again by the liquid flow dyeing machine at a dyeing temperature of 60℃for 60 minutes, followed by a soaping at 80℃for 10 minutes. After dyeing and drying, the fabric was impregnated with an aqueous solution containing 1 wt% of a silicon-based softener, subjected to padding at a padding ratio of 80%, dried at 150℃for 1 minute, subjected to a treatment for providing a hand feeling by an air drum at 80℃for 30 minutes at a speed of 700 m/min, and finally subjected to setting at 130℃for 1 minute, to thereby obtain a dyed fabric having a warp density of 153 yarns/2.54 cm and a weft density of 104 yarns/2.54 cm. The warp yarn of the cuprammonium rayon taken out of the fabric had a degree of polymerization of 84dtex/45 filaments of 440.
Comparative example 4
The warp yarn and the weft yarn are made of copper ammonium rayon yarn 84dtex/45 long yarn with the polymerization degree of 580 and the tensile strength of 2.3cN/dtex in drying, and a twill fabric with 2/1 structure, which is composed of 144 warp yarns/2.54 cm and 100 weft yarns/2.54 cm, is woven. The obtained grey cloth was fibrillated by a liquid flow dyeing machine at 100℃for 60 minutes with 50g/L of 75% phosphoric acid, dyed by a liquid flow dyeing machine again at a dyeing temperature of 60℃for 60 minutes with an ammonium cuprammonium rayon, and then soaped at 80℃for 10 minutes. After dyeing and drying, the fabric was impregnated with an aqueous solution containing 1 wt% of a silicon-based softener, subjected to padding at a padding ratio of 80%, dried at 150℃for 1 minute, subjected to a treatment for providing a hand feeling by an air drum at 80℃for 30 minutes at a speed of 700 m/min, and finally subjected to setting at 130℃for 1 minute, to thereby obtain a dyed fabric having a warp density of 153 yarns/2.54 cm and a weft density of 104 yarns/2.54 cm. The warp yarn of the cuprammonium rayon taken out of the fabric had a degree of polymerization of 84dtex/45 filaments of 400.
Comparative example 5
The warp yarn and the weft yarn are made of copper ammonium rayon yarn 84dtex/45 long yarn with the polymerization degree of 580 and the tensile strength of 2.3cN/dtex in drying, and a twill fabric with 2/1 structure, which is composed of 144 warp yarns/2.54 cm and 100 weft yarns/2.54 cm, is woven. The obtained grey cloth was fibrillated by 30g/L of 35% aqueous hydrogen peroxide solution at 100℃for 60 minutes using a flow dyeing machine, dyed for 60 minutes by a copper ammonium rayon at a dyeing temperature of 60℃again using a flow dyeing machine, and then soaped at 80℃for 10 minutes. After dyeing and drying, the fabric was impregnated with an aqueous solution containing 1wt% of a silicon-based softener, subjected to padding at a padding ratio of 80%, dried at 150℃for 1 minute, subjected to a treatment for providing a hand feeling by an air drum at 80℃for 30 minutes at a speed of 700 m/min, and finally subjected to setting at 130℃for 1 minute, to thereby obtain a dyed fabric having a warp density of 153 yarns/2.54 cm and a weft density of 104 yarns/2.54 cm. The warp threads of the cuprammonium rayon taken out of the fabric had a degree of polymerization of 84dtex/45 filaments of 180.
Comparative example 6
The warp yarn and the weft yarn are made of copper ammonium rayon yarn 84dtex/45 long yarn with the polymerization degree of 580 and the tensile strength of 2.3cN/dtex in drying, and a twill fabric with 2/1 structure, which is composed of 144 warp yarns/2.54 cm and 100 weft yarns/2.54 cm, is woven. The obtained grey cloth was fibrillated at 130℃for 45 minutes using an air flow dyeing machine at 6.4g/L with acetic acid, dyed for 360 minutes at a dyeing temperature of 60℃with an air flow dyeing machine again, and then soaped at 80℃for 10 minutes. After dyeing and drying, the fabric was impregnated with an aqueous solution containing 1wt% of a silicon-based softener, subjected to padding at a padding ratio of 80%, dried at 150℃for 1 minute, subjected to a treatment for providing a hand feeling by an air drum at 100℃for 30 minutes at a speed of 900 m/min, and finally subjected to setting at 130℃for 1 minute, to thereby obtain a dyed fabric having a warp density of 153 yarns/2.54 cm and a weft density of 104 yarns/2.54 cm. The warp threads of the cuprammonium rayon taken out of the fabric had a degree of polymerization of 84dtex/45 filaments of 190.
The fabrics obtained in examples 1 to 4 and comparative examples 1 to 6 were evaluated for the degree of fibrillation and the amount of change in fibrillation degree and hand feeling due to washing, with respect to a sample fabric washed 10 times by the above-described washing test method and a sample fabric not subjected to the washing. Further, the modified and fibrillated copper ammonium rayon 84dtex/45 filaments and the organic solvent cellulose fiber 89dtex/30 filaments were taken out from the fabric samples of examples 1 to 4, and the non-modified or fibrillated copper ammonium rayon 84dtex/45 filaments and the organic solvent cellulose fiber 89dtex/30 filaments were taken out from the fabric samples of comparative examples 1 to 6, and the tensile strength of the warp yarn at the time of drying was measured. Table 1 below summarizes the raw materials, the modifying treatment, and the fibril treatment of the sample filaments used in examples 1 to 4 and comparative examples 1 to 6, and the evaluation results are shown in table 2 below.
TABLE 1
TABLE 2
It was found that the fabrics using modified cellulose fibers of examples 1 to 4 had good touch with softness and rebound feeling without any change in fibril feel due to washing, and had tensile strength exceeding 1.0cN/dtex. That is, examples 1 to 4 had a washing, characteristic surface feel, softness and a feel with rebound feel, and were excellent in durability of the washing surface feel and feel.
In contrast, the fabrics of comparative examples 1 to 6 had tensile strengths of 1.0cN/dtex or less, were subjected to fibril removal at the stage before washing, or had a polymerization degree of more than 250, and had fibril shedding and a change in the degree of fibrillation after washing. That is, in comparative examples 1 to 6, the change in the surface feel and the hand feel due to washing was large, or the strength as a fabric could not be maintained, the pores were generated due to abrasion during wearing or washing, or the fibrils were removed at the stage before washing, so that it was not suitable as a fibril-containing fiber product requiring good hand feel.
Industrial applicability
The present invention can provide regenerated cellulose fibers having a characteristic surface feel, softness and a feel with a rebound feel, which are easily fibrillated by rubbing/kneading in a wet state, and which are excellent in the durability of the surface feel and feel against water washing, and fabrics using the same, and therefore the present invention is industrially applicable.
Description of the reference numerals
1A state in which a fibril aggregate mainly composed of cellulose microfibrils is fibrillated in the fiber axis direction (fibrillated state)
2 Cellulose microfibrils
Claims (18)
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| JPH08291481A (en) * | 1995-04-18 | 1996-11-05 | Toyobo Co Ltd | Dyeing of combined fiber woven or knit fabric containing regenerated cellulose-based fiber |
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| NL246561A (en) * | 1958-12-31 | |||
| GB9103297D0 (en) * | 1991-02-15 | 1991-04-03 | Courtaulds Plc | Fibre production method |
| JP3269143B2 (en) | 1992-11-27 | 2002-03-25 | 東洋紡績株式会社 | Composite fiber woven / knitted fabric excellent in texture and method for producing the same |
| JP3267746B2 (en) * | 1993-06-07 | 2002-03-25 | 東洋紡績株式会社 | Method for producing composite fiber woven / knitted fabric |
| GB9412500D0 (en) * | 1994-06-22 | 1994-08-10 | Courtaulds Fibres Holdings Ltd | Fibre manufacture |
| GB9412501D0 (en) * | 1994-06-22 | 1994-08-10 | Courtaulds Fibres Holdings Ltd | Manufacture of fibre |
| JPH08113846A (en) | 1994-08-22 | 1996-05-07 | Toyobo Co Ltd | Fabric excellent in body, stiffness and soft touch feeling and its production |
| JP3578227B2 (en) * | 1994-10-17 | 2004-10-20 | 東洋紡績株式会社 | Easy fibrillated polynosic fiber and method for producing the same |
| JP3611350B2 (en) * | 1994-11-09 | 2005-01-19 | 旭化成せんい株式会社 | Circular knit with excellent color appearance |
| JPH11315474A (en) * | 1998-04-28 | 1999-11-16 | Unitika Ltd | Fibrillation of fabric comprising solvent-spun cellulose fiber |
| GB2399094A (en) | 2003-03-04 | 2004-09-08 | Tencel Ltd | Treatment of lyocell containing fibres/fabrics with aqueous carboxylic acid at above atmospheric pressure & elevated temperature, prior to dyeing & tumbling |
| AT515693B1 (en) * | 2014-10-29 | 2015-11-15 | Chemiefaser Lenzing Ag | Fast fibrillating lyocell fibers and their use |
| EP3536851A1 (en) | 2018-03-06 | 2019-09-11 | Lenzing Aktiengesellschaft | Lyocell fiber with increased tendency to fibrillate |
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