JP4858184B2 - Side-by-side type cellulose fatty acid mixed ester composite fiber - Google Patents

Description

The present invention relates to a side-by-side cellulose fatty acid mixed ester composite fiber having latent high crimpability and a fabric using the same.
More specifically, the present invention relates to a side-by-side cellulose fatty acid mixed ester composite fiber having a specific composite ratio in a side-by-side composite fiber composed of a cellulose fatty acid mixed ester composition and polyester.

  Cellulose ester fiber is a fiber having excellent characteristics not found in synthetic fibers such as polyester and polyamide. In other words, it has been positioned as a high-grade garment application because it has many characteristics as a garment fiber such as elegant luster, deep color tone, color developability, dry feeling and moisture absorption.

  In recent years, in the garment field, there has been a demand for fibers that are superior in handling properties, and have a softer bulkiness, softness, and the like, due to diversification of consumer needs and the desire to upgrade.

  However, since cellulose ester fibers are inferior in synthetic fiber and shrinkage properties, it is difficult to impart bulkiness or the like, but in recent years, the following proposals have been made.

For example, Patent Documents 1 to 3 propose latent crimpable acetate fibers that can express a soft soft texture and a large swell. Here, two types of acetate having different acetylation degrees are side-by-side type composite dry spinning, and then the cellulose component of the acetate component having a low acetylation degree is celluloseized to generate a yarn length difference to express crimp characteristics. Although the fiber has excellent crimp characteristics, since one side of the composite fiber is celluloseized, the fabric using the fiber loses the pleat (eg, durability of the pleat) after being wet. ), Reduced dimensional stability, and wrinkles remained. Further, due to the characteristics of the cellulose ester polymer, there is a concern that fibrillation is likely to occur due to rubbing in the dyeing process due to strength reduction under wet conditions and rubbing in washing.
On the other hand, Patent Document 4 proposes an acetate composite entangled yarn rich in swell. Here, after the acetate yarn and the polyester yarn are entangled to form a composite entangled yarn, a hot water treatment at 90 to 130 ° C. is performed. By doing so, the polyester yarn contracts and moves to the core of the composite yarn, and the bulkiness is expressed by making the loop and sagging of the acetate yarn remarkable. The fiber is excellent in bulkiness and uses polyester yarn, so it has excellent pleat durability (holding property), dimensional stability, anti-wrinkle properties, etc. under wet conditions, but in terms of soft texture. It was still insufficient.
Thus far, cellulosic fibers excellent in soft texture and bulkiness and excellent in various properties of the fabric under wet conditions have not been obtained.
JP-A-7-109622 JP-A-8-3820 JP-A-7-102419 JP-A-11-350270

  The present invention is intended to solve the above-described conventional problems, and provides a side-by-side cellulose fatty acid mixed ester composite fiber excellent in crimp characteristics. Furthermore, it is providing the fabric which is excellent in the soft feeling and plump feeling using this fiber, and has the favorable performance also in wet condition.

  As a result of intensive studies in order to solve the above-mentioned problems, the inventors of the present invention are fibers comprising a composition (A) and a polyester (B) mainly composed of a cellulose fatty acid mixed ester, and a composite ratio thereof. (A) / (B) is found to exhibit excellent crimp characteristics by heat-treating a side-by-side cellulose fatty acid mixed ester composite fiber having an area ratio of 80/20 to 20/80, and uses the fiber. As a result, the present inventors have succeeded in obtaining a fabric having a soft texture and a feeling of large swelling, and completed the present invention.

  That is, the gist of the present invention is as follows.

  1st invention of this invention is a fiber which consists of a composition (A) which uses cellulose fatty acid mixed ester as a main component, and polyester (B), Comprising: The composite ratio (A) / (B) is area ratio 80. / 20-20 / 80 is a side-by-side cellulose fatty acid mixed ester composite fiber.

  The second invention is the side-by-side cellulose fatty acid mixed ester composite fiber according to the first invention, wherein the cellulose fatty acid mixed ester is cellulose acetate propionate and / or cellulose acetate butyrate.

  A third invention is the side-by-side cellulose fatty acid mixed ester composite fiber according to the first or second invention, wherein the polyester is polypropylene terephthalate and / or polybutylene terephthalate.

  A fourth invention is the side-by-side cellulose fatty acid mixed ester composite fiber according to any one of the first to third inventions, wherein the crimp rate is 5 to 40%.

  A fifth invention is a fabric comprising at least a part of the side-by-side cellulose fatty acid mixed ester composite fiber described in any one of the first to fourth inventions.

  The side-by-side type cellulose fatty acid mixed ester composite fiber of the present invention has good crimp characteristics. The fabric using the fibers has a soft feeling and a large swelling feeling, and is suitable for clothing use.

  Hereinafter, the side-by-side cellulose fatty acid mixed ester composite fiber of the present invention will be described in detail.

  The side-by-side cellulose fatty acid mixed ester composite fiber of the present invention is a fiber composed of a composition (A) and a polyester (B) mainly composed of a cellulose fatty acid mixed ester, and its composite ratio (A) / (B ) Is 80/20 to 20/80 in area ratio.

  The side-by-side type composite fiber of the present invention refers to a composite fiber in which the compositions (A) and (B) are bonded together along the fiber length direction.

  The component on one side of the side-by-side type cellulose fatty acid mixed ester composite fiber in the present invention is a composition containing a cellulose fatty acid mixed ester as a main component. Cellulose fatty acid mixed ester is a cellulose fatty acid mixed ester in which three hydroxyl groups present in cellulose glucose units are blocked with two or more acyl groups, and from the viewpoint of yarn-manufacturability and cost of side-by-side type composite fibers. Are preferably cellulose acetate propionate having an acetyl group and a propionyl group, and cellulose acetate butyrate having an acetyl group and a butyryl group. In this case, the average substitution degree of the acetyl group and the acyl group (propionyl group or butyryl group) preferably satisfies the following formula. The average degree of substitution refers to the number of chemically bonded acyl groups among the three hydroxyl groups present per glucose unit of cellulose.

2.2 ≦ (average degree of substitution of acetyl group + average degree of substitution of acyl group) ≦ 2.9
The cellulose fatty acid mixed ester satisfying the above formula has good miscibility with the plasticizer, and the melt spinnability and the spinning manipulability in the composite spinning are remarkably improved. In addition, the crimping properties and mechanical properties of the composite fiber can be improved, and when the fabric is made, the pleat retention and wrinkle resistance are improved, and further, the strength reduction width when wet is reduced. preferable.

  The weight average molecular weight of the cellulose fatty acid mixed ester is preferably from 5 to 300,000, more preferably from 80 to 270,000, from the viewpoints of mechanical properties of the fiber, yarn-manufacturability, and thermal decomposition resistance of the polymer. More preferably, it is ˜250,000.

  The composition mainly composed of cellulose fatty acid mixed ester in the present invention may contain a plasticizer. From the viewpoints of yarn maneuverability and the mechanical properties and crimp properties of the resulting fiber, the plasticizer content is preferably 5 to 25% by weight, more preferably 8 to 22% by weight, and 10 to 20% by weight. % Is more preferable.

  The plasticizer is preferably a polyhydric alcohol compound, specifically, a polyalkylene glycol or glycerin compound having good compatibility with a cellulose fatty acid mixed ester and a remarkable thermoplastic effect capable of melt spinning. , Caprolactone compounds and the like, and polyalkylene glycol is particularly preferable.

  Specific examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol having a weight average molecular weight of 200 to 4000, but are not limited thereto, and these can be used alone or in combination.

  The composition containing the cellulose fatty acid mixed ester as a main component in the present invention preferably contains a phosphorus-based antioxidant, and a pentaerythritol-based compound is particularly preferable. When a phosphorus-based antioxidant is contained, the effect of preventing thermal decomposition of the cellulose fatty acid mixed ester is very remarkable even in a high spinning temperature range and a low discharge region, and the deterioration of the mechanical properties of the fiber is suppressed, The color tone of the resulting fiber is improved. The compounding amount of the phosphorus-based antioxidant is preferably 0.005% by weight to 0.500% by weight with respect to the melt spinning composition.

  The cellulose fatty acid mixed ester in the present invention has a matting agent, a deodorant, a flame retardant, a yarn friction reducing agent, a coloring inhibitor, a coloring pigment, a dye, an antistatic agent, an antibacterial agent, an ultraviolet ray as long as its physical properties are not impaired. As necessary, inorganic fine particles and organic compounds can be contained as an absorbent, an infrared absorber, a crystal nucleating agent, a fluorescent brightening agent, and the like.

  The component (B) on the other side of the side-by-side type cellulose fatty acid mixed ester composite fiber in the present invention is a polyester, which is a fiber-forming polyester having good interfacial adhesion with the cellulose fatty acid mixed ester and stable yarn-manufacturability. There is no particular limitation as long as it is present. However, in order to have a good mechanical feeling when made into fiber mechanical characteristics, chemical characteristics, crimp characteristics, and fabric, polypropylene terephthalate (hereinafter abbreviated as PPT) or polybutylene terephthalate (hereinafter referred to as (Abbreviated as PBT).

  Here, the polypropylene terephthalate (PPT) of the present invention is a polyester obtained using terephthalic acid as the main component and 1,3-propanediol as the main glycol component, and the polybutylene terephthalate (PBT) is terephthalic acid. Polyester obtained by using 1,4-butanediol as a main glycol component as a main component, and both PPT and PBT contain a copolymer component capable of forming other ester bonds at a ratio of 20 mol% or less good. Examples of copolymerizable compounds include dicarboxylic acids such as isophthalic acid, succinic acid, cyclohexanedicarboxylic acid, adipic acid, dimer acid, sebacic acid, 5-sodium sulfoisophthalic acid, ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol Diols such as polyethylene glycol and polypropylene glycol can be exemplified, but the invention is not limited thereto. Further, if necessary, titanium dioxide as a matting agent, silica or alumina fine particles as a lubricant, hindered phenols, coloring pigments as an antioxidant may be added.

  Regarding the side-by-side type cellulose fatty acid mixed ester composite fiber of the present invention, the composite ratio (A) / (B) of the composition (A) and the polyester (B) mainly composed of a cellulose fatty acid mixed ester is 80 / in area ratio. 20-20 / 80. By setting the composite ratio of the A component and the B component within the above range, sufficient crimping characteristics are exhibited, and when used as a fabric, pleat retention and wrinkle resistance are improved, and yarn maneuverability is stabilized. Can be made. In the composite ratio (A) / (B), when the ratio of the A component is greater than 80% and less than 20%, the difference in melt viscosity between the two components becomes too large, and as a result, immediately below the discharge hole of the spinneret. A yarn bending phenomenon occurs, which not only causes a decrease in fiber characteristics and crimp characteristics, but also makes the spinning process unstable, and sometimes the spinning composition adheres to the spinneret and makes it difficult to operate. . Furthermore, when the component A is greater than 80%, the shrinkage stress is reduced, so that the fabric feeling using the composite fiber is greatly reduced, and the wrinkle resistance (characteristic that is difficult to wrinkle) and the pleat retention property are reduced. End up. On the other hand, when the ratio of the component A is less than 20%, not only the characteristics derived from the cellulose-based polymer are lost, but also the shrinkage becomes too large, and the coarseness of the fabric using the composite fiber is increased. The composite ratio (A) / (B) is more preferably 75/25 to 25/75, and still more preferably 70/30 to 30/70.

  The crimp rate of the side-by-side type cellulose fatty acid mixed ester composite fiber of the present invention is 5 to 40%. The present inventors paid attention to the fact that, for example, the ability to develop crimps under fabric restraint is important, heat treatment was performed by the following method, and the crimp rate was defined by the following formula (1). This equation is also used in, for example, Japanese Patent No. 3485070.

(1) Crimp rate (%) = [(L0−L1) / L0] × 100
L0: Boiling water treatment is performed for 15 minutes in a state where a 0.9 × 10 ⁻³ cN / dtex load is suspended on the fiber casserole, air-dried, and further subjected to 150 ° C. dry heat treatment for 15 minutes, and then the heat treatment load is removed. Case length when 180 × 10 ⁻³ cN / dtex load is hung L1: Case length when L0 measurement is removed and L0 measurement load is removed and 0.9 × 10 ⁻³ cN / dtex load is hung again By hanging the same load as 0.9 × 10 ⁻³ cN / dtex corresponding to the restraining force inside the fiber case and heat-treating it, the crimp expression ability under the constraint of the fabric is expressed by the crimp rate of the fiber case. It can be expressed. The higher the crimp ratio, the higher the crimp expression ability. If it is 5% or more, it is possible to give an appropriate swell and soft feeling as the object of the present invention. The crimp rate is preferably 10% or more. When the crimp rate is less than 5%, the stretchability is insufficient, and when used for a fabric, there is almost no difference from the case of using a normal cellulose fatty acid mixed ester fiber, and the fabric intended by the present invention is obtained. I can't. On the other hand, if the crimping ratio exceeds 40%, the cloth has a large wiping feeling and a feeling of tightening becomes large, resulting in a rough feeling.

  In addition, the shrinkage stress is important in order to overcome the strong twist and the binding force of the fabric and to stably develop the crimp. The higher the shrinkage stress, the deeper the crimp structure at the intersection of the fabric. Has an excellent feeling of swelling. Further, the maximum value of the shrinkage stress is preferably 0.05 cN / dtex or more, more preferably 0.10 cN / dtex or more, and further preferably 0.15 cN / dtex or more.

  In addition, the higher the temperature at which the shrinkage stress is maximized, the easier the process control in the heat setting process of the fabric, and the fabric can be made into a high-grade fabric without generating wrinkles or streaks. In order to improve crimp expression in the process, the temperature is preferably 80 to 200 ° C. When the temperature is lower than 80 ° C., for example, the shrinkage in the drying process such as the gluing process or the twisting set process becomes large, and the shrinkage difference tends to occur between the inner and outer fibers wound around the beam and between adjacent fibers. As a result, shrinkage spots are generated and the quality of the fabric is lowered. On the other hand, when the temperature is higher than 200 ° C., it is necessary to increase the heat setting temperature, and the fabric becomes hard because it approaches the heat softening temperature of the cellulose fatty acid ester. The temperature at which the shrinkage stress is maximized is more preferably 90 ° C to 190 ° C, and further preferably 100 to 180 ° C.

The strength of the side-by-side cellulose fatty acid mixed ester composite fiber of the present invention is preferably 0.5 cN / dtex or more. If the strength is 0.5 cN / dtex or more, it is preferable because it is easy to pass through high-order processing steps such as weaving and knitting, and the strength of the final product is not insufficient. From the viewpoint of good strength characteristics, the higher the strength, the better, but 0.7 cN / dtex or more is more preferable, and 0.9 cN / dtex or more is more preferable.
The elongation of the side-by-side cellulose fatty acid mixed ester composite fiber of the present invention is preferably 10% or more. When the elongation is 10% or more, fluff does not occur in the spinning process, and fluff and yarn breakage do not occur frequently in high-order processing processes such as weaving and knitting. Becomes better. The elongation is more preferably 13% or more, and further preferably 15% or more.

  The fineness variation value (U%) of the side-by-side type cellulose fatty acid mixed ester composite fiber of the present invention is preferably 2.0% or less. The fineness variation value (U%) is an index of thickness unevenness in the fiber longitudinal direction, and can be obtained by a Worcester tester manufactured by Zerbegger Worcester. If the fineness fluctuation value (U%) is 2.0% or less, it means that the uniformity in the longitudinal direction of the fiber is excellent. When processing into a woven or knitted fabric, no fluff or yarn breakage occurs, and dyeing is performed. Even if it is performed, defects such as strong dye spots and dyed streaks do not occur, and a high-quality woven or knitted fabric is obtained. Moreover, the shrinkage | contraction spot of the fiber at the time of making a fabric can be suppressed, and the beautiful fabric surface can be obtained. The fineness variation value (U%) is preferably as small as possible, more preferably 1.8% or less, and still more preferably 1.5% or less. The measurement conditions for the fineness variation value (U%) will be described in detail in the examples.

  The fiber cross-sectional shape of the side-by-side type cellulose fatty acid mixed ester composite fiber of the present invention may be any of a round cross-section, a triangular cross-section, a multi-lobe cross-section, a flat cross-section, and other known cross-sectional shapes. Therefore, a semicircular side-by-side with a round cross-section, a triangular cross-section side-by-side for the purpose of dry texture, etc. are preferably used.

  Next, the manufacturing method of the side-by-side type | mold cellulose fatty acid mixed ester type composite fiber of this invention is demonstrated. FIG. 1 is a diagram showing an embodiment of an apparatus used in the method for producing a core-sheath composite fiber of the present invention.

  After the polyester and cellulose fatty acid mixed ester compositions are separately melted in the extruder 1 and weighed by the metering pump 2, they are sent to the spinning pack 4 incorporated in the spinning block 3, and the polymer is filtered in the pack. After being bonded to the side-by-side structure with the spinneret 5, the yarn is discharged to obtain a yarn. The spun yarn 6 is once cooled and solidified by a cooling device 7, and then an oil agent is applied by an oil supply guide 8, entangled appropriately by an entanglement device 9, then taken up by a godet roll 10, and a godet roll 11 Then, the wound yarn (side-by-side type cellulose fatty acid mixed ester composite fiber) 13 can be obtained. In addition, you may install a 2-20 cm heating cylinder and a heat retention cylinder under a spinneret as needed in order to improve a spinning property and a mechanical characteristic.

  Alternatively, the yarn 13 once wound may be manufactured by a two-step method, or may be manufactured by a direct spinning drawing method in which the yarn 13 is drawn after being drawn by the godet roll 10.

  The fabric using at least a part of the side-by-side type cellulose fatty acid mixed ester composite fiber of the present invention is a conventional weaving and knitting process after twisting the side-by-side type cellulose fatty acid mixed ester composite fiber depending on the purpose of use. It is obtained through And the side-by-side type | mold cellulose fatty acid mixed ester type composite fiber of this invention expresses crimp by the heat processing of a dyeing | staining process. As a result, the fabric using the side-by-side cellulose fatty acid mixed ester composite fiber of the present invention has an excellent swell feeling. In addition, since the polyester component and the cellulose fatty acid mixed ester component are soft even after being dyed, a fabric having a soft texture can be obtained. Further, the fabric has characteristics under wet conditions (pleat retention, prevention of pleats). It also has excellent wrinkle properties.

  When forming a fabric using at least a part of the side-by-side cellulose fatty acid mixed ester composite fiber, it is necessary to use the side-by-side cellulose fatty acid mixed ester composite fiber as a main component. In other words, only side-by-side cellulose fatty acid mixed ester composite fibers are used as a fabric, or when the fabric is composed of a plurality of types of fibers, the side-by-side cellulose fatty acid mixed ester composite is among the plurality of fibers constituting the fabric. It is necessary to increase the fiber mixing ratio first or second.

  When weaving and knitting using the side-by-side cellulose fatty acid mixed ester composite fiber of the present invention, examples of the knitted fabric include flat knitting, rubber knitting, pearl knitting, double-sided knitting (smooth), tricot, etc. Examples include plain weave, oblique weave, and satin weave, but are not limited thereto.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, each characteristic value in an Example was calculated | required with the following method.

A. Intrinsic Viscosity 0.8 g of the material was dissolved in 10 ml of orthochlorophenol (hereinafter abbreviated as OCP), the relative viscosity ηr was determined using an Ostwald viscometer at 25 ° C., and IV was calculated.

B. Average substitution degree of cellulose fatty acid mixed ester 0.9 g of dried cellulose fatty acid mixed ester dried at 80 ° C. for 8 hours was weighed and dissolved by adding 35 ml of acetone and 15 ml of dimethyl sulfoxide, and further 50 ml of acetone was added. While stirring, 30 ml of 0.5N sodium hydroxide aqueous solution was added and saponified for 2 hours. After adding 50 ml of hot water and washing the side of the flask, it was titrated with 0.5N sulfuric acid using phenolphthalein as an indicator. Separately, a blank test was performed in the same manner as the sample. The supernatant of the solution after titration was diluted 100 times, and the composition of the organic acid was measured using an ion chromatograph. From the measurement result and the acid composition analysis result by ion chromatography, the substitution degree was calculated by the following formula.

TA = (B−A) × F / (1000 × W)
DSace = (162.14 × TA) / [{1− (Mwace− (16.00 + 1.01)) × TA} + {1− (Mwacy− (16.00 + 1.01)) × TA} × (Acy / Ace)]
DSacy = DSace × (Acy / Ace)
TA: Total organic acid amount (ml)
A: Sample titration (ml)
B: Blank test titration (ml)
F: titer of sulfuric acid W: sample weight (g)
DSace: average substitution degree of acetyl group DSacy: average substitution degree of acyl group Mwash: molecular weight of acetic acid Mwacy: molecular weight of other organic acids Acy / Ace: molar ratio of acetic acid (Ace) to other organic acids (Acy) 162 .14: Molecular weight of the repeating unit of cellulose 16.00: Atomic weight of oxygen 1.01: Atomic weight of hydrogen Measurement of Weight Average Molecular Weight of Cellulose Fatty Acid Mixed Ester A sample was completely dissolved in tetrahydrofuran, and a weight average molecular weight was calculated in terms of polystyrene using a gel permeation chromatography 2690 manufactured by Waters.

D. Strength and elongation Under an environment of temperature 20 ° C. and humidity 65%, an autograph AG-50NISMS type manufactured by Shimadzu Corporation was used and a tensile test was performed under the conditions of a sample length of 20 cm and a tensile speed of 20 cm / min to show the maximum load. The value obtained by dividing the point stress (cN) by the initial fineness (dtex) was taken as the tensile strength (cN / dtex). The elongation at that time was defined as elongation (%). The number of measurements was 5 times, and the average values were taken as tensile strength and elongation.

E. Fineness variation (U%)
The U% measurement (normal mode) was obtained by measuring under the following conditions using a Worcester tester 4-CX manufactured by Zerbegger Worcester. The number of measurements was 5, and the average value was U%.

Measurement speed: 200 m / min Measurement time: 2.5 minutes Measurement fiber length: 500 m
Twist: S twist, 12000 / m
F. Crimp rate After carrying out boiling water treatment for 15 minutes in a state where a load of 0.9 × 10 ⁻³ cN / dtex is hung on the fiber casserole, it is air-dried and further subjected to 160 ° C. dry heat treatment for 15 minutes. When the heat treatment is completed, the processing load is removed, and the 180 × 10 ⁻³ cN / dtex load is suspended and held for 30 seconds, then the lash length L0 is measured, the load is quickly removed and the load is held for 5 minutes, and then 0.9 × 10 ^-3 Suspend cN / dtex load and hold for 30 seconds, and then measure lash length L1. The crimp rate was calculated from the obtained casket lengths L0 and L1 by the following formula.

Crimp rate (%) = [(L0−L1) / L0] × 100
G. Shrinkage stress and peak temperature It measured using the KE-2 heat shrinkage stress measuring apparatus by Kanebo Engineering. For measurement, create a ring with a circumference of 20 cm by tying the yarn, and after mounting it on the device, draw the temperature change of the shrinkage stress on the chart under the conditions of initial load 0.01 cN / dtex and temperature increase rate 2.2 ° C / sec. It was. The peak maximum value of the shrinkage stress at this time was taken as the shrinkage stress, and the temperature at that time was taken as the peak temperature. The number of measurements was 5, and the average value was defined as the shrinkage stress value (cN / dtex) and the peak temperature (° C.).

H. Evaluation of soft feeling and swell feeling Using a woven fabric composed of composite fibers, sensory evaluation was performed by 10 panelists, and the evaluation was performed according to the following criteria.

A: It is determined that 9 or more are excellent. ○: 7 to 8 are determined to be excellent. Δ: 5 to 6 are determined to be excellent. X: Less than 5 are determined to be excellent. Evaluation of Pleated Durability A woven fabric made of a composite fiber was folded in half and ironed at 0.4 kg / cm ² × 130 ° C. × 30 seconds to give pleats. Thereafter, the pleated fabric was stirred and washed for 5 minutes in a household washing machine, and the remaining state of the pleat after washing was evaluated according to the following criteria. Only ○ was accepted.

      ○: Clearly pleats remain.

      Δ: Slight pleats remain.

      ×: Almost disappeared pleats.

J. et al. Wrinkle evaluation A fabric made of a composite fiber was stirred and washed for 5 minutes in a household washing machine, washed, and then air-dried overnight on a clothesline, and then the wrinkle condition was evaluated according to the following criteria. Only ○ was accepted.

      ○: Wrinkles are not seen at all.

      Δ: Slight wrinkles are observed.

      X: Many wrinkles occur.

Synthesis example 1
To 100 parts by weight of cellulose (cotton linter), 240 parts by weight of acetic acid and 67 parts by weight of propionic acid were added and mixed at 50 ° C. for 30 minutes. After the mixture was cooled to room temperature, 172 parts by weight of acetic anhydride cooled in an ice bath and 168 parts by weight of propionic anhydride were added as an esterifying agent, and 4 parts by weight of sulfuric acid was added as an esterification catalyst, followed by stirring for 150 minutes. An esterification reaction was performed. In the esterification reaction, when it exceeded 40 ° C., it was cooled in a water bath. After the reaction, a mixed solution of 100 parts by weight of acetic acid and 33 parts by weight of water was added as a reaction terminator over 20 minutes to hydrolyze excess anhydride. Thereafter, 333 parts by weight of acetic acid and 100 parts by weight of water were added, and the mixture was heated and stirred at 80 ° C. for 1 hour. After completion of the reaction, an aqueous solution containing 6 parts by weight of sodium carbonate was added, and the precipitated cellulose acetate propionate was filtered off, subsequently washed with water, and dried at 60 ° C. for 4 hours. The average substitution degree of acetyl group and propionyl group of the obtained cellulose acetate propionate (CAP) was 1.9 and 0.7, respectively, and the weight average molecular weight (Mw) was 177,000.

Examples 1-2
82% by weight of CAP prepared in Synthesis Example 1, 17.9% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol as a phosphorus-based antioxidant Diphosphite 0.1% by weight was kneaded at 240 ° C. using a biaxial extruder and cut to about 5 mm to obtain cellulose fatty acid mixed ester composition pellets (Mw 16,000,000).

  This cellulose fatty acid mixed ester composition (A) and PPT (B) (inherent viscosity IV = 1.50) are melted separately, and a spinneret having a side-by-side structure at a spinning temperature of 265 ° C. (discharge hole diameter: 0.5 mm) Were discharged at a composite ratio shown in Table 1. The spun yarn is cooled and solidified with a cooling device having a cooling length of 1 m using a cooling air with an air temperature of 20 ° C. and a wind speed of 0.5 m / sec. After applying and converging and applying confounding, it is taken up by the first godet roller (speed 1850 m / min), and is wound on the winder via the second godet roller that rotates at the same speed as the first godet roller. Rolled up.

  The physical properties of the fibers obtained in both Examples 1 and 2 were extremely good.

  The obtained side-by-side type composite fiber (100 dtex-24 filament) was used for warp and weft to weave a taffeta fabric having a warp density of 120 / 2.54 cm and a weft density of 95 / 2.54 cm in an air jet loom. This taffeta fabric was scoured by a conventional method (temperature 70 ° C., time 20 minutes), and then subjected to hot water treatment at 100 ° C. for 30 minutes.

  The fabrics obtained in Examples 1 and 2 were very soft and swelled, and pleated durability and wrinkle evaluation results were good.

Examples 3-4
Eastman Chemical Co. cellulose acetate propionate (CAP482-20, acetyl group substitution degree 0.1, propionyl group substitution degree 2.5) 90% by weight and polyethylene glycol (PEG 600) 10% by weight with an average molecular weight of 600 are biaxial. It knead | mixed at 210 degreeC using the extruder, and it cut to about 5 mm, and obtained the cellulose-ester composition pellet (Mw183,000).

  This cellulose fatty acid mixed ester composition (A) and PBT (B) (inherent viscosity IV = 0.82) are melted separately, and a spinneret having a side-by-side structure at a spinning temperature of 250 ° C. (discharge hole diameter: 0.5 mm) Were discharged at a composite ratio shown in Table 1. The spun yarn is cooled and solidified with a cooling device having a cooling length of 1 m using a cooling air with an air temperature of 20 ° C. and a wind speed of 0.5 m / second, and an oil agent is applied using a lubricating device at a position 1800 mm below the spinneret. After applying and converging and applying confounding, it is taken up by the first godet roller (speed 2500 m / min), and is fed to the winder via the second godet roller that rotates at the same speed as the first godet roller. Rolled up. The crimp characteristics of the obtained fiber were good.

  The obtained side-by-side type composite fiber (100 dtex-24 filament) was used for warp and weft to weave a taffeta fabric having a warp density of 120 / 2.54 cm and a weft density of 95 / 2.54 cm in an air jet loom. This taffeta fabric was scoured by a conventional method (temperature 70 ° C., time 20 minutes), and then subjected to hot water treatment at 100 ° C. for 30 minutes.

  The fabric obtained in Example 3 had a good soft texture and an excellent swell feeling. Moreover, the pleat durability and the wrinkle evaluation result were favorable.

  The fabric obtained in Example 4 had a good soft texture and a feeling of swelling, and the pleated durability and wrinkle evaluation results were also good.

Example 5
Eastman Chemical's cellulose acetate butyrate (CAB171: acetyl group substitution degree 1.0, butyryl group substitution degree 1.7) 87% by weight and polyethylene glycol (PEG 600) 13% by weight with an average molecular weight of 600. The mixture was kneaded at 220 ° C. and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 17.3 million).

  This cellulose fatty acid mixed ester composition (A) and PPT (B) (inherent viscosity IV = 1.18) are melted separately, and a spinneret having a side-by-side structure at a spinning temperature of 260 ° C. (discharge hole diameter: 0.5 mm) Were discharged at a composite ratio shown in Table 1. The spun yarn is cooled and solidified with a cooling device having a cooling length of 1 m using a cooling air with an air temperature of 20 ° C. and a wind speed of 0.5 m / second, and an oil agent is applied using a lubricating device at a position 1800 mm below the spinneret. After applying and converging and applying confounding, it is picked up by the first godet roller (speed: 2000 m / min), and passed through the second godet roller that rotates at the same speed as the first godet roller. Rolled up. The crimp characteristics of the obtained fiber were good.

  The obtained side-by-side type composite fiber (100 dtex-24 filament) was used for warp and weft to weave a taffeta fabric having a warp density of 120 / 2.54 cm and a weft density of 95 / 2.54 cm in an air jet loom. This taffeta fabric was scoured by a conventional method (temperature 70 ° C., time 20 minutes), and then subjected to hot water treatment at 100 ° C. for 30 minutes.

  The obtained fabric had excellent soft feeling and swell feeling. Moreover, the pleat durability and the wrinkle evaluation result were favorable.

Comparative Examples 1-2
Composite spinning was performed in the same manner as in Example 1 except for the composite ratios shown in Table 2.

  A woven fabric was prepared in the same manner as in Example 1 using the obtained conjugate fiber. The fabric of Comparative Example 1 was excellent in the swelled feeling, but it was worn out. Moreover, since the shrinkage force was too high, the cloth had a rough feeling and the soft feeling was inferior. Pleated durability and wrinkle evaluation results were good.

  On the other hand, the fabric of Comparative Example 2 had a low crimping rate because the shrinkage stress was too low, and the feeling of swelling was inferior. The pleat durability and the wrinkle evaluation were slightly inferior.

Comparative Example 3
Except for the composite ratios shown in Table 2, spinning was performed in the same manner as in Example 1 to prepare a woven fabric. Since the evaluated fiber was a cellulose acetate propionate single yarn, the crimp characteristics were inferior, and the resulting fabric had no feeling of swelling.

Comparative Example 4
Cellulose triacetate with an average degree of acetylation of 61.6% and cellulose diacetate with an average degree of acetylation of 55.2% were dissolved in a mixed solvent of methylene chloride / methanol (weight ratio 91/9), respectively, and the concentration of cellulose triacetate was 21% by weight. A spinning stock solution and a cellulose diacetate concentration of 21% by weight were prepared. Using these spinning dope solutions, the cellulose diacetate component and the cellulose triacetate component were side-by-side composite spun at a composite ratio of 35:65 by weight by a dry spinning method to obtain a composite fiber precursor.

  Next, a woven fabric was prepared in the same manner as in Example 1 using the obtained composite fiber precursor, and then immersed in an alkaline aqueous solution (1 wt% NaOH aqueous solution, bath ratio 1: 100, temperature 60 ° C., time 10 minutes). Thus, an acetate composite fiber was obtained. The obtained acetate composite fiber was an acetate composite fiber in which cellulose (acetation degree 0%) and cellulose triacetate having an average acetylation degree 61.6% were combined side by side at a weight ratio of 25:75.

  Further, the fabric had excellent soft feeling and swell feeling. However, when the pleat durability was evaluated, the pleat almost disappeared and the pleat durability was inferior. Moreover, when wrinkle evaluation was carried out, many wrinkles were generated.

  The latent crimpable side-by-side type cellulose fatty acid mixed ester composite fiber can be suitably used for applications that require softness and a swelled sensation, including fibers for clothing.

It is a figure which shows one embodiment of the melt spinning apparatus used for the manufacturing method of the side by side type | mold cellulose fatty acid mixed ester type composite fiber of this invention.

Explanation of symbols

1. Extruder 2. 3. Metering pump Spinning block 4. Spin pack 5. Spinneret 6. Spinning yarn 7. Cooling device 8. 8. Lubrication device Confounding device 10. First godet roll 11. Second godet roll 12. Winder 13. Winding yarn

Claims (5)

  It is a fiber comprising a composition (A) comprising a cellulose fatty acid mixed ester as a main component and a polyester (B), and the composite ratio (A) / (B) is 80/20 to 20/80 in area ratio. Side-by-side type cellulose fatty acid mixed ester composite fiber.   The side-by-side cellulose fatty acid mixed ester composite fiber according to claim 1, wherein the cellulose fatty acid mixed ester is cellulose acetate propionate and / or cellulose acetate butyrate.   3. The side-by-side type cellulose fatty acid mixed ester composite fiber according to claim 1, wherein the polyester is polypropylene terephthalate and / or polybutylene terephthalate.   The side-by-side type cellulose fatty acid mixed ester composite fiber according to any one of claims 1 to 3, wherein the crimp rate is 5 to 40%.   A fabric comprising at least a part of the side-by-side type cellulose fatty acid mixed ester composite fiber according to any one of claims 1 to 4.

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