JP4687473B2 - Cellulose fatty acid ester fiber and method for producing the same - Google Patents

Description

  The present invention relates to a cellulose fatty acid ester fiber capable of obtaining an excellent swell feeling and tightness when made into a fabric, and a method for producing the same.

  Cellulose-based materials such as cellulose esters and cellulose ethers are currently attracting a great deal of attention as biomass materials that are most produced on the earth and as biodegradable materials in natural environments.

  Known cellulose-based filaments include regenerated cellulose fibers such as viscose and cupra, and cellulose acetate fibers such as cellulose diacetate and cellulose triacetate. None of these fibers can be fiberized by a melt spinning method because the composition does not have thermoplasticity, or the temperature at which thermoplasticization occurs is equal to or higher than the thermal decomposition temperature, and a solvent is used. Manufactured by a wet or dry spinning method. While these fibers are derived from cellulose, they have very good properties as clothing fibers, such as good gloss and moisture absorption and release, while environmental spinning because they are solution spinning using harmful organic solvents. Concerned.

  For this reason, for the purpose of reducing the environmental burden and improving productivity by the melt spinning method, a technique for performing melt spinning by adding a plasticizer to the cellulose ester resin to improve the thermal fluidity below the thermal decomposition temperature of the resin. It is disclosed (see Patent Document 1).

  The fiber obtained by the above method had a very low shrinkage stress and a very small shrinkage rate in boiling water. That is, since it is very excellent in dimensional stability, it was impossible to obtain a fabric having an excellent swell and tightness even if the fiber was used as a fabric (see Patent Document 1).

On the other hand, Japanese Patent Application Laid-Open No. 2004-176201 discloses a method for producing a fiber that can obtain a fabric having tension and waist. The fabric having fibers obtained here certainly has good tension and waist, but is not excellent in terms of swelling (see Patent Document 2).
JP 2004-27378 A (first page) JP 2004-176201 A (pages 8-9)

  An object of the present invention is to provide a cellulose fatty acid ester fiber that solves the above-mentioned problems of the prior art and obtains a product having an excellent swell feeling and tension when formed into a fabric.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a cellulose fatty acid ester fiber having excellent shrinkage characteristics by performing melt spinning and then stretching under specific conditions. Succeeded in getting. Moreover, by melt spinning a cellulose fatty acid ester composition comprising a specific maleimide copolymer, cellulose fatty acid ester fibers having excellent shrinkage characteristics were obtained, and the present invention was completed. That is, the gist of the present invention is as follows.

  The first invention of the present invention is a composition comprising at least 55% by weight to 95% by weight of a cellulose fatty acid ester in which at least a part of the acyl group has 3 to 18 carbon atoms and 5% by weight to 25% by weight of a plasticizer. The cellulose fatty acid ester fiber is characterized in that the heat shrinkage peak stress is 0.02 cN / dtex or more and the boiling water shrinkage is 5.0% or more.

  According to a second aspect of the present invention, there is provided a composition comprising at least 75% by weight to 95% by weight of a cellulose fatty acid ester having at least part of an acyl group having 3 to 18 carbon atoms and 5% by weight to 25% by weight of a plasticizer. This is a method for producing a cellulose fatty acid ester fiber, wherein the product is melt-spun and then drawn to 1.02 to 2.00 times and then wound without being heat-treated.

  In addition, the third invention of the present invention is a cellulose fatty acid ester in which at least a part of the acyl group has 3 to 18 carbon atoms, 55 wt% to 94 wt%, plasticizer 5 wt% to 25 wt%, and maleimide copolymer. A method for producing cellulose fatty acid ester fibers, comprising melt-spinning a composition comprising at least 1% by weight to 20% by weight.

  Since the cellulose fatty acid ester fiber of the present invention satisfies specific requirements for the heat shrinkage peak stress and the boiling water shrinkage rate, the cellulose fatty acid ester fiber has an excellent swell and tension.

  Moreover, according to the method for producing a cellulose fatty acid ester fiber of the present invention, a fiber having excellent shrinkage characteristics can be obtained by adopting specific stretching conditions after melt spinning.

  Further, according to the method for producing cellulose fatty acid ester fiber of the present invention, a fiber having excellent shrinkage characteristics can be obtained by melt spinning a cellulose fatty acid ester composition comprising a specific maleimide copolymer.

  Hereinafter, the fiber which consists of a composition which contains the cellulose fatty acid ester and plasticizer of this invention at least is demonstrated in detail.

  The cellulose fatty acid ester fiber of the present invention contains cellulose fatty acid ester in the range of 55% by weight to 95% by weight. This is because, when the content of the cellulose fatty acid ester is 55% by weight or more, the vivid coloring property and the hygroscopic property of the fiber made of the cellulose fatty acid ester composition are effectively expressed. It is preferably 65% by weight or more, and more preferably 75% by weight or more.

  In the cellulose fatty acid ester in the present invention, at least a part of the acyl group has 3 to 18 carbon atoms. When at least a part of the acyl group has 3 to 18 carbon atoms, the compatibility with the plasticizer is good, and addition of a small amount of the plasticizer is preferable because the composition exhibits heat fluidity capable of being melt-spun.

  Specific examples of the cellulose fatty acid ester in which at least a part of the acyl group has 3 to 18 carbon atoms include cellulose acetate propionate, cellulose propionate, cellulose acetate butyrate, and cellulose butyrate. Cellulose acetate propionate in which an acetyl group having 2 carbon atoms in an acyl group and a propionyl group having 3 carbon atoms are bonded to cellulose, and an acetyl group having 2 carbon atoms in an acyl group and 4 carbon atoms in cellulose Cellulose acetate butyrate to which a certain butyryl group is bonded has moderate hygroscopicity and good compatibility with a plasticizer, so that at least a part of the acyl group is a cellulose fatty acid ester having 3 to 18 carbon atoms. Is cellulose acetate propionate and cellulose acetate. Tobuchireto is preferable.

  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.

2.0 ≦ (average degree of substitution of acetyl group + average degree of substitution of acyl group) ≦ 3.0
1.5 ≦ (average degree of substitution of acetyl group) ≦ 2.5
0.5 ≦ (Average substitution degree of acyl group) ≦ 1.5
Cellulose fatty acid mixed esters satisfying the above formula are preferable because they have excellent compatibility with plasticizers and, by adding a small amount of plasticizer, heat fluidity capable of melt spinning is expressed. Furthermore, even in the case of a fabric, it is preferable because the heat softening temperature is high and it has appropriate hygroscopicity.

  It is preferable that the weight average molecular weight (Mw) of the cellulose fatty acid ester in which at least a part of the acyl group has 3 to 18 carbon atoms is 50,000 to 255,000. When Mw is less than 50,000, the mechanical properties (particularly strength) of the cellulose fatty acid ester fiber obtained by melt spinning do not reach a practical level, which is not preferable. When Mw is larger than 2550,000, the melt viscosity becomes very high, so that stable fiberization by the melt spinning method cannot be performed. From the viewpoint of good mechanical properties and stable melt spinnability, Mw is more preferably 60,000 to 20,000, and even more preferably 80,000 to 20,000,000. In addition, a weight average molecular weight (Mw) means the value computed by GPC measurement, and demonstrates in detail in an Example.

  The plasticizer content is 5.0% to 25.0% by weight. By setting the content of the plasticizer to 5.0 wt% to 25.0 wt%, the thermal fluidity of the cellulose fatty acid ester is improved, so that fiber formation by melt spinning is possible, thereby reducing the fiber cross section. It can be precisely and arbitrarily controlled, and the mechanical properties of the resulting fiber are also good.

  When the content of the plasticizer is less than 5.0% by weight, the heat fluidity of the composition becomes poor, so that melt fracture occurs during melt spinning, and the obtained fiber characteristics become poor. Furthermore, stable fiberization by the melt spinning method becomes difficult.

  When the content of the plasticizer is more than 25.0% by weight, the thermal fluidity of the composition is improved, but the plasticizer contained in the fiber obtained by spinning may ooze out from the fiber surface, and this is caused by that. As a result, a feeling of slime is generated and a high-quality product cannot be obtained. Furthermore, the strength of the obtained fiber is very low, and the passability in higher processing steps such as weaving and knitting is deteriorated. The plasticizer content is more preferably 8.0 wt% to 22.0 wt%, and most preferably 10.0 wt% to 20.0 wt%.

  The plasticizer in the present invention is preferably a polyhydric alcohol plasticizer or a polycarboxylic acid plasticizer, more preferably a polyhydric alcohol plasticizer, but is not limited thereto.

  The polyhydric alcohol plasticizer that can be specifically used in the present invention has good compatibility with a cellulose fatty acid ester in which at least a part of the acyl group has 3 to 18 carbon atoms, and the thermoplasticization of the cellulose fatty acid ester. Examples include polyalkylene glycols that exhibit significant effects, compounds having a glycerin skeleton, caprolactone compounds, and the like, among which polyalkylene glycols are preferred.

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

  Examples of the polyvalent carboxylic acid plasticizer that can be used in the present invention include polyvalent carboxylic acid esters. Examples of the polyvalent carboxylic acid ester include adipic acid ester, sebacic acid ester, and citric acid ester.

  In the present invention, after melt spinning a thermoplastic composition mainly composed of a cellulose fatty acid ester, the plasticizer contained in the fiber is eluted by chemical treatment using water such as warm water or hot water or an organic solvent. May be. It is preferable to elute the plasticizer because the strength of the final product is not insufficient and the heat softening temperature is increased.

  The cellulose fatty acid ester fiber in the present invention can contain a maleimide copolymer. The maleimide copolymer used in the present invention is a copolymer containing maleimides in the main chain. The copolymer is preferably a copolymer of maleimides with at least one selected from styrene, acrylonitrile, methyl methacrylate, and olefins. The maleimide is preferably phenylmaleimide.

  From the viewpoint of fluidity, the copolymerization ratio of maleimides in the maleimide copolymer preferably used in the present invention is preferably 30% by weight to 80% by weight, more preferably 30% by weight to 50% by weight. is there.

  Moreover, it is preferable that the glass transition point (Tg) of a maleimide-type copolymer is 150 to 220 degreeC. The glass transition point (Tg) is more preferably 180 ° C. or higher, and more preferably 200 ° C. or higher. Moreover, 210 degrees C or less is preferable from a dispersible viewpoint with a cellulose fatty acid ester.

  As the maleimide copolymer, for example, “DENKA IP” (registered trademark) (electrochemical product) is known as a commercially available product, and these can be preferably used in the present invention.

  In the present invention, the content of the maleimide copolymer is preferably 1% by weight to 20% by weight. By containing 1% by weight or more, the shrinkage characteristics of the cellulose fatty acid ester fiber can be favorably expressed. Preferably it is 5 weight% or more. Further, it is preferable to contain 20% by weight or less because the fiber characteristics of the cellulose fatty acid ester fiber are improved. Preferably it is 15 weight% or less, More preferably, it is 10 weight% or less.

  The cellulose fatty acid ester in the present invention preferably contains a phosphite coloration inhibitor. When the phosphite-based anti-coloring agent is contained, the anti-coloring effect is very remarkable even in the range where the spinning temperature is high, and the color tone of the resulting fiber becomes good.

  It is preferable that the compounding quantity of a phosphite type | system | group coloring inhibitor is 0.005 weight%-0.5 weight% with respect to a composition. A blending amount of 0.005% by weight or more is preferable because coloring of the composition during heating can be suppressed. More preferably, it is 0.01 weight% or more, More preferably, it is 0.05 weight% or more. On the other hand, by setting the blending amount to 0.5% by weight or less, degradation due to cutting the molecular chain of the cellulose ester and lowering the degree of polymerization can be suppressed, and the mechanical properties of the resulting fiber are improved. Therefore, it is preferable. More preferably, it is 0.3 weight% or less, More preferably, it is 0.2 weight% or less.

  The composition used in the present invention contains, in addition to the above-mentioned cellulose fatty acid ester and plasticizer, matting agent, deodorant, defoaming agent, color adjuster, flame retardant, yarn friction reducing agent, antioxidant, and coloring pigment. As an electrostatic agent, an antibacterial agent, an ultraviolet absorber, an infrared absorber, a crystal nucleating agent, a fluorescent brightening agent, a lubricant and the like, inorganic fine particles and organic compounds can be contained as necessary.

  The cellulose fatty acid ester fiber in the present invention has a heat shrinkage peak stress of 0.02 cN / dtex or more and a boiling water shrinkage of 5.0% or more.

  When the heat shrinkage peak stress is 0.02 cN / dtex or more and the boiling water shrinkage rate is 5.0% or more, the fibers are sufficient when weaving and knitting cellulose fatty acid ester fibers and then subjecting them to a dyeing process The crimped structure at the intersection of the woven and knitted fabrics becomes deeper, and the fabric after dyeing has an excellent swell and tension.

  In the present invention, the heat shrinkage peak stress of the cellulose fatty acid ester fiber needs to be 0.02 cN / dtex or more. By setting the heat shrinkage peak stress to 0.02 cN / dtex or more, the setting property of the raw machine is ensured, and a high-quality woven or knitted fabric without wrinkles or wrinkles can be produced. The higher the heat shrinkage peak stress is, the better the setability is, so that it is preferably 0.04 cN / dtex or more, and more preferably 0.06 cN / dtex or more. More preferably, it is 0.1 cN / dtex or more. In the current technology, the thermal shrinkage peak stress is close to the limit of 0.5 cN / dtex, and this value is naturally the upper limit.

  The peak temperature of the maximum heat shrinkage stress is preferably 70 ° C to 200 ° C. When the peak temperature of the maximum heat shrinkage stress is in this range, the process control in the heat setting process of the fabric becomes easy, and a high-quality fabric can be obtained without generating wrinkles and streaks in the fabric. When the peak temperature of the maximum heat shrinkage stress is less than 70 ° C., for example, the shrinkage in the drying process such as the gluing process or the twisting set process becomes large, and the fibers between the inner and outer layers wound around the beam and between adjacent fibers Thus, a difference in shrinkage is likely to occur, shrinkage spots occur, and the fabric quality deteriorates. On the other hand, when the peak temperature of the maximum heat shrinkage stress is higher than 200 ° C., it is necessary to increase the heat setting temperature, and the cloth becomes hard because it approaches the thermosetting temperature of the cellulose fatty acid ester fiber, which is not preferable. In order to further exert the effect of the present invention, the temperature of the maximum heat shrinkage stress peak is more preferably 75 ° C to 190 ° C, and further preferably 80 ° C to 180 ° C. The measurement of heat shrinkage peak stress will be described in detail in Examples.

  In the present invention, the boiling water shrinkage of the cellulose fatty acid ester fiber is 5.0% or more. When the boiling water shrinkage is 5.0% or more, when the fabric is heat-treated, the fibers are sufficiently shrunk, and the fabric after the treatment has an excellent feeling of swelling. The boiling water shrinkage is more preferably 5.2% or more, and further preferably 5.5% or more. The upper limit of the boiling water shrinkage is 15.0%, and if it exceeds 15.0%, the fabric may be cured by excessive shrinkage, which is not preferable.

  The strength of the cellulose fatty acid ester fiber in the present invention is preferably 0.9 cN / dtex to 2.5 cN / dtex. If the strength is 0.9 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 more preferable, but specifically 1.0 cN / dtex to 2.5 cN / dtex is more preferable, and 1.1 cN / dtex to 2.5 cN / dtex. More preferably.

  The elongation of the cellulose fatty acid ester fiber in the present invention is preferably 15% to 35%. When the elongation is 15% or more, fluff does not occur in the spinning process, and fluff and thread breakage do not occur frequently in higher processing steps such as weaving and knitting. The good elongation is more preferably 18% or more, and further preferably 20% or more.

  The initial tensile resistance of the cellulose fatty acid ester fiber in the present invention is preferably 30 cN / dtex or more. When the initial tensile resistance is 30 cN / dtex or more, a fabric having appropriate tension and waist can be obtained when the fabric is used. The initial tensile resistance is more preferably 35 cN / dtex or more, and further preferably 40 cN / dtex or more.

  The fineness variation value (U%) of the cellulose fatty acid ester fiber in the present invention is 3.0% or less. The fineness variation value 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 variation value is 3.0% or less, it means that the uniformity in the longitudinal direction of the fiber is excellent, and when processed into a woven or knitted fabric, no fluff or yarn breakage occurs, and even if dyeing is performed, Defects such as partially strong dyed spots and dyed streaks do not occur, resulting in a high-quality woven or knitted fabric. Furthermore, 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 is preferably as small as possible, more preferably 2.5% or less, still more preferably 2.0% or less, and most preferably 1.5% or less. The measurement conditions for the fineness variation value will be described in detail in Examples.

  The single yarn fineness of the cellulose fatty acid ester fiber in the present invention is preferably 0.5 dtex to 20 dtex. By setting the single yarn fineness to 0.5 dtex to 20 dtex, fibers can be obtained with good spinning properties by the melt spinning method, and due to the appropriate bending rigidity of the fiber structure, it can be used for clothing fabrics that require softness. Can also be applied. The single yarn fineness is more preferably 0.8 dtex to 15 dtex, and still more preferably 1 dtex to 10 dtex.

  The cross-sectional shape of the cellulose fatty acid ester fiber in the present invention is not particularly limited, and may be a perfect circular circular cross section, and may be a multilobal shape, a flat shape, an elliptical shape, a W shape, an S shape, or an X shape. , H-shaped, C-shaped, paddy-shaped, cross-girder, hollow, etc.

  Next, the manufacturing method of the cellulose fatty acid ester fiber of 2nd invention is demonstrated.

  After melt spinning a composition comprising at least 75% to 95% by weight of a cellulose fatty acid ester having at least a portion of acyl groups of 3 to 18 carbon atoms and 5% to 25% by weight of a plasticizer, 1.02 It is important that the film is drawn without being heat-treated after being stretched by a factor of 2.0 to 2.0.

  It is important that the draw ratio is 1.02 to 2.0 times. By setting the draw ratio within this range, the heat shrinkage peak stress of the obtained fiber is sufficiently high, and the strength is improved because the orientation of molecular chains is promoted by the draw stress. If the draw ratio is less than 1.02, only fibers having substantially the same properties as those obtained when the stretch is not performed can be obtained. Due to the properties, the stretching stress becomes very high and is substantially difficult. The draw ratio is more preferably 1.05 times to 1.80 times, and still more preferably 1.08 times to 1.50 times.

  In the present invention, the preheating temperature of the fiber subjected to drawing is preferably 200 ° C. or less. By preheating the fibers at 200 ° C. or lower, deformation during stretching can be performed uniformly, and by making the supply yarn softer, stretching tension can be reduced and stretching can be performed with good operability. it can. From the viewpoint of energy cost during production, the preheating temperature is preferably as low as possible, more preferably 150 ° C. or less, further preferably 100 ° C. or less, and most preferably 50 ° C. or less.

  In the present invention, after stretching, it is important to wind up without heat treatment. Here, the temperature “without heat treatment” refers to a temperature of 40 ° C. or lower. After stretching, a highly shrinkable fiber can be obtained by not performing heat treatment. When the heat treatment is performed after stretching, the heat shrinkage rate is reduced by the relaxation action of the fiber due to heat, so that the fiber of the present invention cannot be obtained.

  In the present invention, in order to simplify the process of obtaining the target fiber, after melt spinning, after the spun yarn is taken up by the first godet roller, the first godet roller and the second godet roller You may extend | stretch between godet rollers using a speed difference.

  Alternatively, the undrawn yarn may be taken once by melt spinning and then drawn by a drawing machine. At this time, in order to perform the stretching with low stretching stress using the swelling of the fiber, the unstretched yarn may be stretched after being immersed in a liquid bath such as water or an organic solvent.

  In the present invention, it is preferable that the moisture content of the composition is 0.3% or less during melt spinning. When the moisture content is 0.3% or less, it is possible to stably perform spinning without foaming due to moisture at the time of melt spinning, and the mechanical properties of the resulting multifilament are also good. The moisture content is more preferably 0.2% or less, still more preferably 0.1% or less, and most preferably 0.08% or less.

  In the present invention, the spinning temperature is preferably 220 ° C. to 280 ° C. during melt spinning. By setting the spinning temperature to 220 ° C. or higher, the elongational viscosity of the yarn discharged from the spinneret is sufficiently reduced. Therefore, melt fracture (streamline turbulence occurs when the shear stress of the polymer is high when passing through the spinneret hole. In addition, the occurrence of short pitch periodic spots due to the irregular shape of the yarn discharged from the spinneret does not appear, and uniform fibers can be obtained. Furthermore, since the thinning process of the yarn discharged from the spinneret becomes smooth, the fiber characteristics are good, and the spinning tension does not become excessively high, so that yarn breakage does not occur frequently, and the yarn forming property is stabilized. Moreover, since the thermal decomposition of the composition can be suppressed by setting the spinning temperature to 280 ° C. or less, the mechanical properties are not deteriorated due to a decrease in the molecular weight of the obtained fiber, and the quality is not deteriorated due to coloring. The spinning temperature is more preferably 230 ° C to 270 ° C, and further preferably 240 ° C to 260 ° C.

  In the present invention, at the time of melt spinning, the spinning speed is preferably 500 m / min to 2500 m / min. By setting the spinning speed to 500 m / min to 2500 m / min, the molecular orientation of the obtained fiber is promoted, and a fiber having excellent fiber characteristics can be obtained. The spinning speed is more preferably 750 m / min to 2250 m / min, and most preferably 1000 m / min to 2000 m / min.

  In the present invention, it is important that the cooling air speed is 0.01 m / second or more and 0.50 m / second or less during melt spinning. When the cooling air velocity is within this range, cooling of the single yarn constituting the multifilament discharged from the spinneret becomes uniform, and the resulting fiber has excellent uniformity. The cooling air speed is more preferably 0.10 m / sec or more and 0.45 m / sec or less, and further preferably 0.20 m / sec or more and 0.40 m / sec or less.

  Hereinafter, the present invention will be specifically described with reference to the drawings.

  1-3 is a figure which shows one embodiment of the apparatus used for the manufacturing method of the cellulose fatty acid ester fiber of this invention.

  In FIG. 1, 1 is a spin block, 2 is a melt spinning pack, 3 is a spinneret, 4 is a cooling device, 5 is a spun yarn, 6 is an oiling device, 7 is a first godet roller, and 8 is a second gode. It is a dead roller.

  The molten composition is extruded from the pores of the spinneret 3 attached to the lower part of the melt spinning pack 2 attached to the spin block 1. The extruded spun yarn 5 is cooled to room temperature by the cooling device 4, the finishing agent is applied by the oil supply device 6, and the first godet roller 7 and the second godet roller 8 are rotated at a predetermined speed. Then, the undrawn yarn package 9 is wound by the winder. At this time, using the peripheral speed ratio between the first godet roller 7 and the second godet roller 8, the drawn yarn 10 may be obtained by drawing at a predetermined draw ratio between the rollers.

  The undrawn yarn 9 is then supplied to a drawing step and drawn by a drawing machine as shown in FIG. In the drawing machine, the undrawn yarn is heated on the supply roller 11 set to a predetermined temperature, and drawn to a predetermined fineness using a peripheral speed ratio between the supply roller 11 and the drawing roller 12. The fiber exiting the drawing roller 12 is wound up as a drawn yarn pann 13 while being twisted by a spindle.

  As shown in FIG. 3, a liquid bath 14 may be installed between the supply roller and the stretching roller for the purpose of reducing the stretching stress.

  Next, the manufacturing method of the cellulose fatty acid ester fiber of 3rd invention is demonstrated.

  At least a part of the acyl group contains 55 to 94% by weight of a cellulose fatty acid ester having 3 to 18 carbon atoms, 5 to 25% by weight of a plasticizer, and 1 to 20% by weight of a maleimide copolymer. It is important to melt spin the composition of

  These components may be kneaded before performing melt spinning using a twin-screw kneader or the like, or may be mixed using a static mixer or the like when performing melt spinning.

  The details of the maleimide copolymer used in the present invention are the same as described above.

  The content of the maleimide copolymer used in the present invention is required to be 1 to 20% by weight. By including 1% by weight or more, including 1% by weight or more has an effect of expressing the shrinkage characteristics of cellulose fatty acid ester fibers containing a maleimide copolymer. Preferably it is 5 weight% or more. Moreover, by containing 20 weight% or less, the heat fluidity | liquidity of a cellulose-fatty-acid ester composition improves and the fiber which has favorable thread | yarn physical property can be obtained. Preferably it is 15 weight% or less, More preferably, it is 10 weight% or less.

  The effect of the present invention is manifested by using a maleimide copolymer. By using a maleimide-based copolymer, a fiber having good shrinkage characteristics can be obtained without melt-spinning without stretching by 1.02 to 2.00 times after melt spinning. Can do. The reason is not clear, but it is presumed that the maleimide copolymer has an interaction with the cellulose fatty acid ester and has a rigid structure, so that it is appropriately dispersed in the cellulose fatty acid ester.

  The details of the cellulose fatty acid ester are the same as described above. Cellulose fatty acid esters are contained in an amount of 55 to 94% by weight. When the content of the cellulose fatty acid ester is 55% by weight or more, the vivid coloring property and the hygroscopic property of the fiber made of the cellulose fatty acid ester composition are effectively expressed, and 94% by weight or less of the maleimide copolymer. This is because the contraction rate expression effect is remarkably exhibited. 65 weight% or more is preferable and 75 weight% or more is more preferable.

  The details of the plasticizer used in the present invention are the same as described above. In the present invention, a composition containing 5.0% by weight to 25.0% by weight of a plasticizer is melt-spun. When the content is 5.0% by weight or more, the thermal fluidity of the composition is improved, and stable fibers can be obtained by the melt spinning method. Moreover, by making the content of the plasticizer 25.0% by weight or less, the plasticizer contained in the fiber obtained by spinning can ooze out on the fiber surface, and the slime caused by it can be suppressed. You can get a product. The plasticizer content is more preferably 8.0 wt% to 22.0 wt%, and most preferably 10.0 wt% to 20.0 wt%.

  Moreover, this cellulose fatty acid ester composition may contain the phosphite type | system | group coloring inhibitor mentioned above, and may contain the other resin and additive in the range which does not impair the main point of invention.

  In the present invention, it is preferable to dry the cellulose fatty acid ester composition before melt spinning, so that the moisture content of the composition is 0.3% or less. When the moisture content is 0.3% or less, at the time of melt spinning, it can be stably spun without foaming due to moisture, and the mechanical properties of fibers such as multifilaments obtained are also good. . The moisture content is more preferably 0.2% or less, still more preferably 0.1% or less, and most preferably 0.08% or less.

  In the present invention, the cellulose fatty acid ester composition is melt-spun to obtain fibers. By performing melt spinning, it is possible to form a fiber structure sufficiently developed from the melted state of the cellulose fatty acid ester composition to cooling and solidification, and the environmental load is small and the productivity is excellent. As a melt spinning method, for example, extrusion using an apparatus or an extruder shown in FIG. 1 can be employed as a suitable means.

  The spinning temperature in melt spinning is preferably in the range of 220 ° C to 280 ° C. By setting the spinning temperature to 220 ° C. or higher, the elongational viscosity of the fiber yarn discharged from the spinneret is sufficiently lowered, so that melt fracture (streamline turbulence occurs when the shear stress of the polymer is high when passing through the spinneret hole). This is a phenomenon in which periodic spots of short pitch due to occurrence and a phenomenon that the shape of the yarn discharged from the spinneret becomes irregular) do not appear, and uniform fibers can be obtained. Furthermore, since the thinning process of the fiber yarn discharged from the spinneret becomes smooth, the fiber characteristics are good, and the spinning tension does not become excessively high, so that the yarn does not break frequently and the spinning property is stabilized. Moreover, since the thermal decomposition of the cellulose fatty acid ester composition can be suppressed by setting the spinning temperature to 280 ° C. or lower, the mechanical properties are not deteriorated due to the decrease in the molecular weight of the obtained fiber, and the quality is not deteriorated due to coloring. The spinning temperature is more preferably 230 ° C to 270 ° C, and even more preferably 240 ° C to 260 ° C.

  The method for taking the spun fiber is not particularly limited, and it may be taken using a rotating roller, or may be collected by a net or the like. The spinning speed in the case of taking up using a roller is preferably 500 m / min to 3000 m / min. By setting the spinning speed to 500 m / min to 3000 m / min, it is possible to form a developed fiber structure, and fibers having excellent fiber characteristics can be obtained. The spinning speed is more preferably 1000 m / min to 2500 m / min. Moreover, after drawing a fiber, you may extend | stretch continuously and may wind up.

  In the present invention, the plasticizer can be eluted after melt-spinning the thermoplastic composition mainly composed of cellulose fatty acid ester. The elution of the plasticizer is preferably performed in any step until the fiber obtained by melt spinning becomes a final product such as clothing. For the elution of the plasticizer, the plasticizer contained in the fiber may be eluted by a chemical treatment using water such as warm water or hot water or an organic solvent.

  The most preferred example of the method for producing the cellulose fatty acid ester fiber of the present invention has an average substitution degree of acetyl group of 1.8 to 2.4 and an average substitution degree of propionyl group of 0.5 to 0.8. Cellulose acetate propionate having a weight average molecular weight (Mw) of 80,000 to 20,000,000 to 85% by weight, polyethylene glycol having an average molecular weight of 200 to 4000, 10 to 25% by weight, 3 to 10% by weight of a polymer and 0.05 to 0.2% by weight of a phosphite anti-coloring agent are melt-kneaded at a temperature of 200 ° C. to 240 ° C. with a biaxial extruder, pelletized, dried, and Using a Luder type spinning machine, melt spinning is performed at a spinning temperature of 240 ° C. to 260 ° C. and a take-up speed of 1000 m / min to 2500 m / min. Rear wound makes with the package.

  As described above, the cellulose fatty acid ester fiber having a heat shrinkage peak stress obtained by the present invention of 0.02 cN / dtex or more and a boiling water shrinkage of 5.0% or more is lightweight, heat retaining, soft Excellent swellability, hygroscopicity, etc., especially when it is made into a fabric, it has an excellent swell and tension, so that it is especially woven such as taffeta, desine, georgette, twill, or knitted fabric such as tengu, smooth, tricot, etc. Suitable for Furthermore, it can be used not only for apparel use but also for various living materials as non-woven fabric use, medical use, sanitary material, and stuffing material.

Hereinafter, the present invention will be described in more detail with reference to examples. In addition, although each characteristic value in an Example was calculated | required with the following method, this invention is not limited to these.
A. Thermal contraction peak stress The thermal contraction peak stress was measured using a KE-2 thermal contraction stress measuring device manufactured by Kanebo Engineering Co., Ltd. For measurement, after creating a ring with a circumference of 20 cm by tying the yarn and mounting it on the device, draw the temperature change of the heat shrinkage stress on the chart under the conditions of initial load 0.01 cN / dtex and temperature increase rate 2.2 ° C / sec. Let The peak value of the heat shrinkage stress at this time was taken as the heat shrinkage peak stress, and the temperature at that time was taken as the peak temperature of the heat shrinkage peak stress. The number of measurements was 5, and the average value was defined as the heat shrinkage peak stress and the peak temperature.
B. Boiling water shrinkage rate A sample is scraped and the sample length L0 is measured under a load of 0.09 cN / dtex, and then treated in boiling water for 15 minutes under no load. After the treatment, the sample was air-dried, the sample length L1 was measured under a load of 0.09 cN / dtex, and calculated using the following formula. The number of measurements was 5, and the average value was defined as the boiling water shrinkage.

Boiling water shrinkage (%) = {(L0−L1) / L0} × 100
C. A point where the maximum load is indicated by performing a tensile test under the conditions of a specimen length of 20 cm and a tensile speed of 20 cm / min using Shimadzu Autograph AG-50NISMS type in an environment of a high elongation temperature of 20 ° C. and a humidity of 65%. The value obtained by dividing the stress (cN) by the fineness (dtex) was taken as the 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 strength and elongation.
D. Initial tensile resistance The initial tensile resistance was calculated based on JIS L 1013: 1999 (chemical fiber filament yarn test method) 8.10.
E. Fineness variation (U%)
U% (Normal) measurement was obtained by measuring under the following conditions using a Worcester tester 4-CX manufactured by Zerbegger Worcester.

Measurement speed: 200 m / min Measurement time: 2.5 minutes Measurement fiber length: 500 m
Twist: S twist, 12000 / min The number of measurements was 5, and the average value was defined as the fineness variation value (U%).
F. Texture characteristics A circular knitted fabric was prepared using cellulose fatty acid ester fibers, and after scouring at 70 ° C. for 20 minutes, dyeing was performed under conditions of a dyeing temperature of 98 ° C. and a dyeing time of 60 minutes. Using this circular knitted fabric, sensory evaluation with tentacles was performed. Evaluate bulge, tension, and waist. “Excellent” is ◎, “Excellent” is ○, “Normal” is △, “Inferior” is ×, and “Excellent” or higher is passed did.
G. Measurement of weight average molecular weight (Mw) by GPC It was completely dissolved in tetrahydrofuran so that the concentration of the cellulose fatty acid ester was 0.15% by weight, and used as a sample for GPC measurement. Using this sample, GPC measurement was performed with Waters 2690 under the following conditions, and the weight average molecular weight (Mw) was determined in terms of polystyrene. The number of measurements was 3 times, and the average value was Mw. Column: Two TSK gel GMHHR-H manufactured by Tosoh Coupling Detector: Waters2410 Differential refractometer RI
Moving bed solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Injection volume: 200 μl
Synthesis example 1
To 100 parts by weight of cellulose (dissolved pulp manufactured by Nippon Paper Industries Co., Ltd.), 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 the acetyl group and propionyl group of the obtained cellulose acetate propionate was 1.9 and 0.7, respectively, and the weight average molecular weight (Mw) was 178,000.

Example 1
82% by weight of cellulose acetate propionate 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 as a phosphite colorant -Methylphenyl) pentaerythritol diphosphite 0.1% by weight was kneaded at 230 ° C. using a biaxial extruder and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 16.00,000).

  The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 570 ppm), melted at a melter temperature of 260 ° C., and introduced into a melt spinning pack having a spinning temperature of 260 ° C. Spinning was performed from a die having 36 holes of 0.23 mmφ−0.60 mmL under the condition of 5 g / min. The spun yarn was cooled with a cooling air of 25 ° C. and a wind speed of 0.25 m / sec, and the oil agent was applied and converged, and then a first godet roller rotating at 1500 m / min (roller surface temperature 26 ° C. ). Then, it wound up with the winder without heat-processing through the 2nd godet roller (roller surface temperature 26 degreeC) rotated at 1650 m / min (drawing ratio 1.10 times).

    The characteristics of the obtained fiber (100 dtex-36 filament) are as shown in Table 1, and the fabric had a very excellent swell feeling and tight waist (see Table 1).

Example 2
80% by weight of cellulose acetate propionate prepared in Synthesis Example 1, 19.9% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, and bis (2,6-di-t-butyl-4 as a phosphite colorant -Methylphenyl) pentaerythritol diphosphite 0.1% by weight was kneaded at 225 ° C. using a biaxial extruder, and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 167,000).

  The pellets were vacuum-dried at 80 ° C. for 8 hours (moisture content after drying: 620 ppm), melted with a single screw extruder and introduced into a melt spinning pack with a spinning temperature of 255 ° C. Spinning was performed from a die having 48 holes of 0.20 mmφ−0.50 mmL under the conditions of 1 g / min. The spun yarn was cooled by cooling air at 25 ° C. and a wind speed of 0.20 m / sec, and after applying an oil agent to converge, a first godet roller rotating at 1715 m / min (roller surface temperature 80 ° C. ). Then, it wound up with the winder without heat-processing through the 2nd godet roller (roller surface temperature 26 degreeC) rotated at 1800 m / min (drawing ratio 1.05 times).

  The characteristics of the obtained fiber (167 dtex-48 filament) were as shown in Table 1, and the fabric had an excellent swell and tension (see Table 1).

Example 3
85% by weight of cellulose acetate propionate prepared in Synthesis Example 1, 14.9% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, and bis (2,6-di-t-butyl-4 as a phosphite colorant -Methylphenyl) pentaerythritol diphosphite 0.1 wt% was kneaded at 235 ° C using a biaxial extruder and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 150,000).

  The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 480 ppm), melted with a single screw extruder, introduced into a melt spinning pack with a spinning temperature of 265 ° C., and a discharge amount of 18. Spinning was performed from a die having 24 holes of 0.25 mmφ−0.50 mmL under the condition of 0 g / min. After passing this spun yarn through a heating cylinder (150 mm, 270 ° C.) installed at a position 110 mm below the spinneret, it was cooled by cooling air having a length of 25 ° C. and a wind speed of 0.30 m / sec. After being applied and converged, the first godet roller rotating at 1200 m / min (roller surface temperature 27 ° C.) is taken up, and then the second godet roller rotating at the same speed as the first godet roller ( It was wound around a winder through a roller surface temperature of 27 ° C.

  This undrawn yarn (150 dtex-24 filament) was brought into contact with the supply roller (roller temperature 25 ° C.) 6 times, the draw ratio was 1.15 times, and the draw roller (roller temperature 25 ° C.) was turned 6 times, and 200 m / Winded up at a speed of minutes.

  The properties of the obtained fibers (130 dtex-48 filaments) are as shown in Table 1, and the fabric had a very excellent swell feeling and tight waist (see Table 1).

Example 4
85% by weight of cellulose acetate propionate prepared in Synthesis Example 1, 14.9% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, and bis (2,6-di-t-butyl-4 as a phosphite colorant -Methylphenyl) pentaerythritol diphosphite 0.1 wt% was kneaded at 235 ° C using a biaxial extruder and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 150,000).

    The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 480 ppm), melted with a single screw extruder, introduced into a melt spinning pack with a spinning temperature of 265 ° C., and a discharge amount of 18. Spinning was performed from a die having 24 holes of 0.23 mmφ−0.46 mmL under the condition of 0 g / min. After passing this spun yarn through a heating cylinder (150 mm, 270 ° C.) installed at a position 110 mm below the spinneret, it was cooled by cooling air having a length of 25 ° C. and a wind speed of 0.30 m / sec. After being applied and converged, the first godet roller rotating at 1200 m / min (roller surface temperature 27 ° C.) is taken up, and then the second godet roller rotating at the same speed as the first godet roller ( It was wound around a winder through a roller surface temperature of 27 ° C.

  This unstretched yarn (150 dtex-24 filament) was brought into contact with the supply roller (roller temperature 100 ° C.) 6 times, the draw ratio was 1.15 times, and the draw roller (roller temperature 25 ° C.) was turned 6 times, and 200 m / Winded up at a speed of minutes.

  The properties of the obtained fibers (130 dtex-48 filaments) are as shown in Table 1, and the fabric had a very excellent swell feeling and tight waist (see Table 1).

Example 5
90% by weight of cellulose acetate propionate (CAP482-20) manufactured by Eastman Chemical Co., Ltd. and 10% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600 are kneaded at 210 ° C. using a biaxial extruder and cut to about 5 mm. Thus, cellulose ester composition pellets (Mw 155,000) were obtained.

  The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 420 ppm), melted at a melter temperature of 240 ° C., and introduced into a melt spinning pack at a spinning temperature of 240 ° C. Spinning was performed from a die having 24 holes of 0.18 mmφ−0.36 mmL under the condition of 5 g / min. The spun yarn was cooled with cooling air at 25 ° C. and a wind speed of 0.35 m / second, and after applying an oil agent to converge, a first godet roller rotating at 1500 m / min (roller surface temperature 28 ° C. ) And wound around a winder via a second godet roller (roller surface temperature 28 ° C.) rotating at the same speed as the first godet roller.

  This unstretched yarn (90 dtex-24 filament) was brought into contact with the supply roller (roller temperature 25 ° C.) 6 times and then immersed in water (water temperature 22 ° C., water bath length 500 mm), and the draw ratio was 1.12 times. The film was wound around the drawing roller (roller surface temperature 25 ° C.) 6 times and wound at a speed of 50 m / min.

  The characteristics of the obtained fiber (80 dtex-24 filament) are as shown in Table 1, and the fabric had an excellent feeling of swelling and tension (see Table 1).

Example 6
90% by weight of cellulose acetate butyrate (CAB381-20) manufactured by Eastman Chemical Co., Ltd. and 10% by weight of polyethylene glycol (PEG600) having an average molecular weight of 600 are kneaded at 205 ° C. using a biaxial extruder and cut to about 5 mm. Cellulose ester composition pellets (Mw 120,000) were obtained.

    The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 510 ppm), melted at a melter temperature of 250 ° C., and introduced into a melt spinning pack having a spinning temperature of 255 ° C. The spinneret was spun from a die having 24 holes of 0.18 mmφ−0.45 mmL under the conditions of minutes. The spun yarn is passed through a heating cylinder (150 mm, 300 ° C.) installed at a position 50 mm below the spinneret, and then cooled by cooling air at 25 ° C. and a wind speed of 0.20 m / sec. The first godet roller rotating at 1095 m / min (roller surface temperature 27 ° C.) is taken up, and then the second godet roller rotating at 1500 m / min (roller surface temperature 27 ° C.). (Stretching ratio: 1.37 times), and wound with a winder without heat treatment.

    The properties of the obtained fiber (100 dtex-24 filament) are as shown in Table 1, and the fabric had an excellent swell and tension (see Table 1).

Example 7
82% by weight of cellulose acetate propionate prepared in Synthesis Example 1, 17.9% by weight of glycerol diacetate monooleate, and bis (2,6-di-t-butyl-4-methylphenyl) as a phosphite colorant Pentaerythritol diphosphite (0.1% by weight) was kneaded at 225 ° C. using a biaxial extruder and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 16,000).

  The pellets were vacuum-dried at 80 ° C. for 8 hours (moisture content after drying: 610 ppm), melted with a single screw extruder, introduced into a melt spinning pack having a spinning temperature of 260 ° C., and a discharge amount of 16. Spinning was performed from a die having 36 holes of 0.23 mmφ−0.60 mmL under the condition of 5 g / min. The spun yarn was cooled with a cooling air of 25 ° C. and a wind speed of 0.25 m / sec, and the oil agent was applied and converged, and then a first godet roller rotating at 1500 m / min (roller surface temperature 26 ° C. ). Then, it wound up with the winder without heat-processing through the 2nd godet roller (roller surface temperature 26 degreeC) rotated at 1650 m / min (drawing ratio 1.10 times).

  The characteristics of the obtained fiber (100 dtex-36 filament) were as shown in Table 1, and the fabric had an excellent swell and tension (see Table 1).

Example 8
77.9% by weight of cellulose acetate propionate produced in Synthesis Example 1, 17.0% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, maleimide copolymer (electrochemical industry “DENKAIP MS-NA” styrene / anhydrous Maleic acid / N-phenylmaleimide = 50.1 / 1.8 / 48.1, MFR (260 ° C.) = 2.5) 5.0% by weight and bis (2,6-di) as a phosphite-based coloring inhibitor -T-Butyl-4-methylphenyl) pentaerythritol diphosphite 0.1% by weight using a biaxial extruder at 230 ° C., cutting to about 5 mm, and cellulose ester composition pellets (Mw 166,000) )

  The pellets were vacuum-dried at 80 ° C. for 8 hours (moisture content after drying: 660 ppm), and a nozzle hole of 0.23 mmφ−0.30 mmL was formed at a spinning temperature of 260 ° C. under a discharge rate of 10.0 g / min. Spinning from a die with 12 holes. After cooling this spun yarn with cooling air at a temperature of 25 ° C. and a wind speed of 0.25 m / sec, applying an oil agent and converging, and then picking it up with a first godet roller rotating at 1000 m / min Winded up with a winder.

  The properties of the obtained fiber (100 dtex-12 filament) are as shown in Table 2, and the fabric had a very excellent swell feeling and tight waist (see Table 2).

Example 9
77.9% by weight of cellulose acetate propionate produced in Synthesis Example 1, 17.0% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, a maleimide copolymer (Nippon Catalyst “Polyimilex (registered trademark) PSX0371 styrene / Maleic anhydride / N-phenylmaleimide = 50.1 / 1.8 / 48.1, MFR (260 ° C.) = 13) 5.0% by weight and bis (2,6-di-) as a phosphite colorant t-butyl-4-methylphenyl) pentaerythritol diphosphite 0.1% by weight using a biaxial extruder at 230 ° C., cutting to about 5 mm, and cellulose ester composition pellets (Mw 165,000) Got.

  The pellets were vacuum-dried at 80 ° C. for 8 hours (moisture content after drying: 450 ppm), and a nozzle hole of 0.23 mmφ−0.30 mmL was formed at a spinning temperature of 260 ° C. under a discharge rate of 10.0 g / min. Spinning from a die with 12 holes. After cooling this spun yarn with cooling air at a temperature of 25 ° C. and a wind speed of 0.25 m / sec, applying an oil agent and converging, and then picking it up with a first godet roller rotating at 1000 m / min Winded up with a winder.

  The characteristics of the obtained fiber (100 dtex-12 filament) were as shown in Table 2, and the fabric had an excellent feeling of swelling and tension (see Table 2).

Example 10
77.9% by weight of cellulose acetate propionate produced in Synthesis Example 1, 17.0% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, maleimide copolymer (electrochemical industry “DENKAIP MS-L2A” styrene / anhydrous Maleic acid / N-phenylmaleimide = 49.7 / 6.2 / 44.1, MFR (260 ° C.) = 2.5) 5.0% by weight and bis (2,6-di) as a phosphite-based coloring inhibitor -T-Butyl-4-methylphenyl) pentaerythritol diphosphite 0.1 wt% was kneaded at 230 ° C. using a biaxial extruder and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 150,000) )

  The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 590 ppm), and a nozzle hole of 0.23 mmφ−0.30 mmL was formed at a spinning temperature of 260 ° C. under a discharge rate of 10.0 g / min. Spinning from a die with 12 holes. After cooling this spun yarn with cooling air at a temperature of 25 ° C. and a wind speed of 0.25 m / sec, applying an oil agent and converging, and then picking it up with a first godet roller rotating at 1000 m / min Winded up with a winder.

  The properties of the obtained fiber (100 dtex-12 filament) are as shown in Table 2, and the fabric had a very excellent swell feeling and tight waist (see Table 2).

Example 11
77.9% by weight of cellulose acetate propionate produced in Synthesis Example 1, 17.0% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, maleimide copolymer (electrochemical industry “DENKAIP MS-NA” styrene / anhydrous Maleic acid / N-phenylmaleimide = 50.1 / 1.8 / 48.1, MFR (260 ° C.) = 2.5) 5.0% by weight and bis (2,6-di) as a phosphite-based coloring inhibitor -T-Butyl-4-methylphenyl) pentaerythritol diphosphite 0.1 wt% was kneaded at 230 ° C. using a biaxial extruder and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 1650,000). )

  The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 600 ppm), and a nozzle hole of 0.23 mmφ−0.30 mmL was formed at a spinning temperature of 260 ° C. under a discharge rate of 10.0 g / min. Spinning from a die with 12 holes. After cooling this spun yarn with cooling air at a temperature of 25 ° C. and a wind speed of 0.25 m / sec, applying an oil agent and converging, and then picking it up with a first godet roller rotating at 1000 m / min Winded up with a winder.

  This undrawn yarn (100 dtex-12 filament) was brought into contact with the supply roller (roller temperature 110 ° C.) 6 turns, the draw ratio was 1.10 times, and the draw roller (roller temperature 110 ° C.) was turned 6 turns, 200 m / Winded up at a speed of minutes.

  The properties of the obtained fiber (91 dtex-12 filament) were as shown in Table 2, and the fabric had an excellent swell and tension (see Table 2).

Example 12
73.8% by weight of cellulose acetate propionate produced in Synthesis Example 1, 16.1% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, a maleimide copolymer (electrochemical industry “DENKAIP MS-NA” styrene / anhydrous Maleic acid / N-phenylmaleimide = 50.1 / 1.8 / 48.1, MFR (260 ° C.) = 2.5) 10.0% by weight and bis (2,6-di) as a phosphite coloration inhibitor -T-Butyl-4-methylphenyl) pentaerythritol diphosphite 0.1% by weight using a biaxial extruder at 230 ° C., cutting to about 5 mm, and cellulose ester composition pellets (Mw 166,000) )

  The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying 580 ppm), and a nozzle hole of 0.23 mmφ−0.30 mmL was formed at a spinning temperature of 260 ° C. under a discharge rate of 10.0 g / min. Spinning from a die with 12 holes. After cooling this spun yarn with cooling air at a temperature of 25 ° C. and a wind speed of 0.25 m / sec, applying an oil agent and converging, and then picking it up with a first godet roller rotating at 1000 m / min Winded up with a winder.

  The properties of the obtained fiber (100 dtex-12 filament) are as shown in Table 2, and the fabric had a very excellent swell feeling and tight waist (see Table 2).

Comparative Example 1
82% by weight of cellulose acetate propionate 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 as a phosphite colorant -Methylphenyl) pentaerythritol diphosphite 0.1% by weight was kneaded at 230 ° C. using a biaxial extruder and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 16.00,000).

  The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 570 ppm), melted at a melter temperature of 260 ° C., and introduced into a melt spinning pack having a spinning temperature of 260 ° C. Spinning was performed from a die having 36 holes of 0.23 mmφ−0.60 mmL under the condition of 5 g / min. The spun yarn was cooled with a cooling air of 25 ° C. and a wind speed of 0.25 m / sec, and the oil agent was applied and converged, and then a first godet roller rotating at 1500 m / min (roller surface temperature 26 ° C. ) And wound up with a winder without heat treatment via a second godet roller (roller surface temperature 26 ° C.) rotating at the same speed as the first godet roller.

The properties of the obtained fiber (110 dtex-36 filament) were as shown in Table 3, and the fabric was inferior in swell and tension (see Table 3).
Comparative Example 2
82% by weight of cellulose acetate propionate 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 as a phosphite colorant -Methylphenyl) pentaerythritol diphosphite 0.1% by weight was kneaded at 230 ° C. using a biaxial extruder and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 16.00,000).

  The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 570 ppm), melted at a melter temperature of 260 ° C., and introduced into a melt spinning pack having a spinning temperature of 260 ° C. Spinning was performed from a die having 36 holes of 0.23 mmφ−0.60 mmL under the condition of 5 g / min. The spun yarn was cooled with a cooling air at 25 ° C. and a wind speed of 0.25 m / sec, and after the oil agent was applied and converged, a first godet roller (roller surface temperature of 26 ° C.) rotating at 1485 m / min. ). Then, it wound up with the winder without heat-processing through the 2nd godet roller (roller surface temperature 26 degreeC) rotated at 1500 m / min (drawing ratio 1.01 times).

The properties of the obtained fiber (110 dtex-36 filament) were as shown in Table 3, and the fabric was inferior in swell and tension (see Table 3).
Comparative Example 3
85% by weight of cellulose acetate propionate prepared in Synthesis Example 1, 14.9% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, and bis (2,6-di-t-butyl-4 as a phosphite colorant -Methylphenyl) pentaerythritol diphosphite 0.1 wt% was kneaded at 235 ° C using a biaxial extruder and cut to about 5 mm to obtain cellulose ester composition pellets (Mw 150,000).

  The pellets were vacuum dried at 80 ° C. for 8 hours (moisture content after drying: 480 ppm), melted with a single screw extruder, introduced into a melt spinning pack with a spinning temperature of 265 ° C., and a discharge amount of 18. Spinning was performed from a die having 24 holes of 0.25 mmφ−0.50 mmL under the condition of 0 g / min. After passing this spun yarn through a heating cylinder (150 mm, 270 ° C.) installed at a position 110 mm below the spinneret, it was cooled by cooling air having a length of 25 ° C. and a wind speed of 0.30 m / sec. After being applied and converged, the first godet roller rotating at 1200 m / min (roller surface temperature 27 ° C.) is taken up, and then the second godet roller rotating at the same speed as the first godet roller ( It was wound around a winder through a roller surface temperature of 27 ° C.

  This unstretched yarn (150 dtex-24 filament) was brought into contact with the supply roller (roller temperature 100 ° C.) 6 turns, the draw ratio was 1.15 times, and the draw roller (roller temperature 140 ° C.) was turned 6 turns, 200 m / Winded up at a speed of minutes.

  The properties of the obtained fiber (130 dtex-48 filament) are as shown in Table 3. Although there was a tight waist, there was almost no swelling (see Table 3).

Comparative Example 4
77.9% by weight of cellulose acetate propionate produced in Synthesis Example 1, 17.0% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, 5.0% by weight of polyester elastomer (“Hytrel” manufactured by Toray DuPont) and As a phosphite-based anti-coloring agent, 0.1% by weight of bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is kneaded at 230 ° C. using a biaxial extruder and about 5 mm. To obtain cellulose ester composition pellets (Mw 164,000).

  The pellets were vacuum-dried at 80 ° C. for 8 hours (moisture content after drying: 330 ppm), and a nozzle hole of 0.23 mmφ−0.30 mmL was formed at a spinning temperature of 260 ° C. under a discharge rate of 10.0 g / min. Spinning from a die with 12 holes. After cooling this spun yarn with cooling air at a temperature of 25 ° C. and a wind speed of 0.25 m / sec, applying an oil agent and converging, and then picking it up with a first godet roller rotating at 1000 m / min Winded up with a winder.

  The properties of the obtained fiber (100 dtex-12 filament) are as shown in Table 3, and the fabric was inferior in swell and tension (see Table 3).

    The obtained fiber has excellent shrinkage characteristics and can be used as a fiber for clothing, an industrial fiber, a nonwoven fabric, and the like, and can be particularly suitably used for a fiber for clothing.

It is process drawing which shows an example of the manufacturing method of the cellulose fatty acid ester fiber of this invention. It is another example of the manufacturing method of the cellulose fatty acid ester fiber of this invention. It is another example of the manufacturing method of the cellulose fatty acid ester fiber of this invention.

Explanation of symbols

1: Spin block 2: Melt spinning pack 3: Spinneret 4: Cooling device 5: Spinning yarn 6: Oil supply device 7: First godet roller 8: Second godet roller 9: Undrawn yarn 10: Stretched yarn 11: Roller 12: Supply roller 13: Stretching roller 14: Stretched yarn pann 15: Liquid bath

Claims (5)

  A fiber comprising a composition comprising at least 55% by weight to 95% by weight of a cellulose fatty acid ester having at least part of an acyl group having 3 to 18 carbon atoms and 5% by weight to 25% by weight of a plasticizer. A cellulose fatty acid ester fiber having a peak stress of 0.02 cN / dtex or more and a boiling water shrinkage of 5.0% or more.   At least a part of the acyl group contains 55 to 94% by weight of a cellulose fatty acid ester having 3 to 18 carbon atoms, 5 to 25% by weight of a plasticizer, and 1 to 20% by weight of a maleimide copolymer. The cellulose fatty acid ester fiber according to claim 1, comprising a composition comprising:   After melt spinning a composition comprising at least 75% to 95% by weight of a cellulose fatty acid ester having at least a portion of acyl groups of 3 to 18 carbon atoms and 5% to 25% by weight of a plasticizer, 1.02 A method for producing a cellulose fatty acid ester fiber, wherein the cellulose fatty acid ester fiber is stretched to 2.00 to 2.00 times and wound without being subjected to heat treatment.   At least a part of the acyl group contains 55 to 94% by weight of a cellulose fatty acid ester having 3 to 18 carbon atoms, 5 to 25% by weight of a plasticizer, and 1 to 20% by weight of a maleimide copolymer. A method for producing a cellulose fatty acid ester fiber according to claim 2, wherein the composition is melt-spun.   A fiber structure comprising the cellulose fatty acid ester fiber according to claim 1 at least partially.

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