JPH11315475A - Man-made cellulose fiber and method for producing the same - Google Patents

Abstract

(57) Abstract: An artificial cellulose fiber which has a high abrasion strength and a low hot water shrinkage rate and is capable of obtaining a crepe woven fabric excellent in embossing property, and obtains the artificial cellulose fiber at low cost. To provide a manufacturing method. SOLUTION: (1) An artificial cellulose fiber treated with a compound having two or more functional groups that reacts with cellulose, wherein the number of frictions before rubbing is 7000 or more and the hot water shrinkage at 100 ° C. Is 2.5% or less, and the degree of crimped orientation of the crepe fabric using the 2,000 T / m twisted yarn of the artificial cellulose fiber as the weft is 0.87.
Man-made cellulose fibers that are: (2) In producing an artificial cellulose fiber by a wet spinning method, a cellulose fiber in an undried state after washing with water reacts with cellulose.
A method for producing an artificial cellulose fiber, comprising applying an aqueous dispersion or solution of a compound having two or more functional groups, and then subjecting it to a heat treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial cellulose fiber and a method for producing the same, and more particularly, to an artificial cellulose fiber having a high abrasion strength, a low hot water shrinkage and a high crimping property. The present invention relates to a cellulose fiber and a method for producing the same.

[0002]

2. Description of the Related Art As a method for imparting wrinkle resistance, shrink resistance and the like to artificial cellulose fibers, a resin processing method of performing intermolecular crosslinking of cellulose is generally employed. This resin processing is mainly performed in a fabric state. In the case of a knitted fabric, after dyeing, steps such as resin liquid impregnation, preliminary drying, curing, soaping, and drying are performed. When such resin processing is performed,
Although the performances such as wrinkle resistance and shrink resistance can be obtained, there is a disadvantage that the abrasion strength of the fabric when dried is lower than that of the unprocessed product. In apparel applications, when the evaluation value by the Martindale method is used as an index as the wear strength, if the number of times of friction is 6,000 or less, there is a high possibility that abrasion will occur during continuous wear, and practically a wear strength of 7000 or more is desired. ing.

In recent years, composite fabrics of cellulose fibers and materials such as esters, nylons, spandex, and acetate have been often used.
Since the entire fabric is impregnated with the resin solution, the use efficiency of the resin solution used is low, leading to an increase in processing cost. Further, there is a problem that the resin liquid adhesion becomes non-uniform due to the fiber entangled points and folded portions of the fabric or knitted structure. For this reason, shrink-prevented artificial cellulose fibers having high abrasion strength and requiring no resin processing after dyeing are desired. Further, Japanese Patent Application Laid-Open No. 6-501994 proposes that, in order to reduce the tendency of fibrillation, resin processing is applied to undried cellulose fibers in the artificial cellulose spinning process. However, in this method, since the cellulose fibers are subjected to resin processing in a bath or in a wet state, energy costs are increased, and in addition, there is a drawback that a fabric obtained from the fibers has insufficient shrink resistance.

[0004]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of resin processing in a fabric or fiber state in the prior art described above, has high wear strength, low hot water shrinkage, and reduces grain standing. An object of the present invention is to provide an artificial cellulose fiber from which an excellent crepe fabric can be obtained and a method for producing the artificial cellulose fiber at low cost.

[0005]

Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies on the resin processing in the process of producing a wet-spun synthetic cellulose, and have found that the cellulose fibers in the undried state during the spinning process have the same properties as the cellulose. A solution or dispersion of a compound having two or more functional groups that react (hereinafter simply referred to as a compound solution) is attached, and a cross-linking between the compound and a cellulose molecular chain is performed by using a drying step indispensable for wet spinning. By doing so, it was found that an artificial cellulose fiber capable of obtaining a crepe fabric excellent in dry abrasion strength and excellent in embossability without obtaining an increase in processing cost was obtained, and the present invention was reached. .

That is, the invention claimed in the present application is as follows. (1) An artificial cellulose fiber treated with a compound having two or more functional groups that reacts with cellulose, the number of rubs to be worn out is 7000 or more, and the hot water shrinkage rate at 100 ° C. is 2.5 % Or less, and the degree of crimped orientation of the crepe fabric using a 2,000 T / m twist of the artificial cellulose fiber as the weft is 0.87 or less. (2) The artificial cellulose fiber according to (1), wherein the compound having two or more functional groups that reacts with cellulose is a compound having a molecular weight of 10,000 or less. (3) The compound having two or more functional groups that reacts with the cellulose is an epoxy compound.
(1) The artificial cellulose fiber according to (1).

(4) Cellulose or derivatized cellulose raw material is dissolved, discharged from a spinning port, coagulated, regenerated, washed with water, and then dried. A method for producing an artificial cellulose fiber, comprising applying an aqueous dispersion or solution of a compound having two or more functional groups that react with cellulose to an undried cellulose fiber, and then subjecting the fiber to a heat treatment. (5) In the heat treatment, the evaporation of water and the reaction of the cellulose fiber with a compound having two or more functional groups that react with cellulose are simultaneously performed (4).
A method for producing the artificial cellulose fiber according to the above. (6) The method for producing an artificial cellulose fiber according to (4) or (5), wherein the compound having two or more functional groups that reacts with cellulose is a compound having a molecular weight of 10,000 or less. (7) The compound having two or more functional groups that reacts with the cellulose is an epoxy compound.
(4) The method for producing an artificial cellulose fiber according to (5).

[0008]

The wet-spun synthetic cellulose fiber is obtained by the steps of dissolving cellulose or a derivatized cellulose material, discharging from a spinneret, coagulating and regenerating, washing with water, drying and winding. The amorphous portion of the undried cellulose fiber obtained after washing in these steps swells and suppresses the formation of hydrogen bonds as compared with that of the dried yarn, and is 2 to 3 times the weight of the cellulose fiber. Contains water inside. When a solution or dispersion of a compound having two or more functional groups that react with cellulose is attached to such undried artificial cellulose fibers after washing with water, the diffusivity of the compound solution into the fibers is compared with that of the dried yarn. It is extremely high and can be uniformly distributed inside the fiber. Table 6 above
Unlike the method described in Japanese Patent No. 501994, the evaporation of water and the reaction between the compound and the cellulose fiber are performed simultaneously in the subsequent drying operation after the application of the compound liquid to the cellulose fiber. And the shrink resistance of the resulting fiber can be improved. Further, in the wound dry yarn, voids are formed inside the amorphous due to the compound molecules diffused inside the fiber, so that a decrease in dyeability can be prevented as compared with the case where the dry yarn is processed with resin. In addition, by quantitatively applying the compound to the fiber in the spinning process, the unevenness in the adhesion of the compound is extremely reduced as compared with the case where the fabric is processed with a resin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Man-made cellulose fibers used in the present invention include, for example, cupra, rayon, polynosic and the like. Pigment, titanium oxide, other natural and synthetic polymer fine particles are added to these fibers. Also those containing agents. The form of the fiber is filament,
Any of staples and tows may be used. Examples of the compound having two or more functional groups that react with cellulose used in the present invention include N-methylol compound, dihydroxyethylene urea, aldehyde, acetal, epoxide, active vinyl compound, aziridinyl compound, polycarboxylic acid, and acid chloride. , Isocyanate compounds, quaternary ammonium compounds, or mixtures thereof.
Among these, epoxy compounds are preferred from the viewpoint of improving the wear strength and the texture of the fabric, and more preferred are diglycidyl ether compounds or polyglycidyl ether compounds of mono- or polyethylene glycol.

In the present invention, from the viewpoint of allowing the compound to penetrate into the fiber sufficiently quickly, it is preferable that the molecular weight of the compound is small, specifically, the molecular weight is preferably 10,000 or less. In addition, a reaction catalyst, a stabilizer and the like corresponding to the compound can be appropriately selected and mixed with the dispersion or solution of the compound. The artificial cellulose fiber of the present invention has a number of rubbing times of at least 7000 times, a hot water shrinkage at 100 ° C. of 2.5% or less, and a twist of 2,000 T / m of the artificial cellulose fiber. The degree of crimped orientation of the crepe fabric used as the weft is 0.8
7 or less. If the number of frictions before the wear is less than 7000 times, practical strength cannot be obtained, and the hot water shrinkage rate is 2.5%.
If it exceeds 300, shrinkproofness of the fabric cannot be obtained, and if the degree of crimping orientation exceeds 0.87, sufficient crimping property cannot be obtained in terms of aesthetics.

[0011] Here, the friction strength is JIS L1018-
It was measured according to the 6.18.5E method of 1990, and the hot water shrinkage ratio was measured in accordance with JIS L1013-1992.
Noh. It was measured according to 15 (1). In addition, the degree of crimping orientation is measured based on the method for measuring crimping property of a crimped fabric described in Japanese Patent Application No. 10-77122. That is, a thread portion detecting step of detecting an outline image from the image of the grain fabric as a thread portion forming the grain fabric by the image analysis device, and an image acquiring the direction of the detected thread portion by the image analysis device. The direction distribution of the yarn obtained from the analysis step and the information processing step of calculating the distribution of the plurality of yarn portions in the obtained direction by the image analysis device is objectively quantified as the degree of undulation of the yarn provided in the crimped fabric. It was done. Specifically, the direction of the yarn axis in a minute section of the warp and the weft constituting the woven fabric is measured using a CCD camera and an image processing device, and the measurement result is quantified and is shown as a crimped orientation degree. The degree of orientation takes a value of 0 to 1, and the lower the value, the higher the graininess. If the difference in the degree of orientation is 0.02, it is recognized as a significant difference even in a sensory test.

The artificial cellulose fiber having such excellent properties is produced by a wet spinning method comprising dissolving a cellulose raw material, discharging from a spinning port, coagulating, regenerating, washing with water, and drying. In the above method, it is necessary to apply an aqueous dispersion or solution of a compound having two or more functional groups that react with cellulose to the undried cellulose fiber after washing with water, and then to perform a heat treatment. In this heat treatment, it is preferable to simultaneously carry out the evaporation of water and the reaction between the cellulose fiber and a compound having two or more functional groups that react with cellulose.

As a method of applying the above-mentioned compound liquid, a known application apparatus used for fabrics and fibers such as a kiss roll type, a pad type, a spray type, and a foam type can be used. After application, the fiber is drawn by passing the yarn through a knife edge or the like in a continuous spinning method, or by squeezing a sheet-like yarn, or by squeezing or centrifuging in a batch-type process such as centre or Hank spinning. It is preferable to remove and reuse the excess compound solution adhering to, and to increase the thermal efficiency of the drying and crosslinking reactions. The adhesion ratio of the compound to the dried yarn is 2-1.
Preferably, it is in the range of 5% by weight. The adhered fraction can be controlled by the concentration of the compound and the contact time between the washed yarn and the compound. The temperature and passage time in the dryer are controlled by the spinning method,
It is determined by the water content of the washed yarn, the reaction start temperature of the compound, the catalyst type, the yarn speed, and the like.
It is 20-200 degreeC, Preferably it is 150-180 degreeC. It is preferable to set the reaction time required for the reaction from the selected reaction temperature.

[0014]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The measurement items shown in the examples were measured by the following methods. (1) Number of frictions before wear (wear strength): A sample yarn was made into a single-knit fabric, and JIS L1018-1990 6.
According to the 18.5E method (knitted dough test method (Martindale method)), the end point until worn out was measured. (2) Hot water shrinkage: Measure the hot water shrinkage at 100 ° C. in accordance with JIS L1013-1992 7.15 (1) (Chemical Fiber Filament Yarn Test Hot Water Shrinkage A Method (Skew Shrinkage)). did.

(3) Degree of embossed orientation: Japanese Patent Application No. Hei.
It measured based on the method of measuring the crimp standing property of the crimped fabric described in No. 0-77122. The apparatus used for this measurement includes photographing means for photographing the textured cloth, thread part detecting means for detecting a contour image in an image obtained by the photographing means as a thread part forming the textured cloth, Image analyzing means for acquiring the direction of the obtained thread portion, and information processing means for calculating the distribution of the acquired direction for the plurality of thread portions.

Example 1 20% by weight of ethylene glycol diglycidyl ether and 1.2% by weight of magnesium borofluoride (acidic catalyst) were added to a cupra yarn (75d / 45f) which had been coagulated and regenerated and washed with water by a wet flow tension spinning method before drying. % And softener 78.
A solution having a composition of 8% by weight was prepared using kiss roll with a cellulose-to-cellulose ratio of 4
1.4 wt% was given, and heat treatment was performed at 150 ° C. for 7 seconds. The hot water shrinkage of the obtained cupra yarn was 1.5%. Using the obtained cupra yarn, the number of frictions until the worn out of a plain knitted fabric knitted by a single knitting machine was 12,000 times. Twist the obtained cupra yarn at 2000 T / m,
This was used as a weft, and a greige crepe (115 warp / inch, 85 weft / inch) greige machine was prepared using a cupra 75d / 45f non-twisted warp as a warp. Crepe decine having a degree of weft crimp standing orientation of 0.86 was obtained.

Example 2 20% by weight of diethylene glycol diglycidyl ether and 1.2% by weight of magnesium borofluoride (acidic catalyst) were added to a cupra yarn (75d / 45f) which had been coagulated and regenerated and washed with water by a wet flow tension spinning method before drying. And soft oil 7
A solution having a composition of 8.8% by weight was applied with kiss roll to a cellulose-to-cellulose ratio of 36.3% by weight, and heat-treated at 150 ° C. for 7 seconds. The hot water shrinkage of the obtained cupra yarn was 2.3%. Using the cupra yarn obtained, the number of frictions until the flat knitted fabric knitted by a single-knitting machine was worn out was 10,500 times. The obtained cupra yarn is twisted at 2,000 T / m, this is used as the weft, and the warp is used as the cupra 75d / 45.
f Using a non-twisted yarn, a greige crepe (having a density of 115 yarns / inch and a weft density of 85 yarns / inch) was prepared and subjected to crimping under a normal prescription. Crepe decine was obtained.

Example 3 20% by weight of ethylene glycol diglycidyl ether and 1.2% by weight of magnesium borofluoride (acidic catalyst) were added to a cupra yarn (40d / 24f) which had been coagulated and regenerated and washed with water by a tension spinning method under a wet flow and washed with water. % And softener 78.
A solution having a composition of 8% by weight was prepared using kiss roll with a cellulose-to-cellulose ratio of 4
0.1 wt% was given, and heat treatment was performed at 150 ° C. for 6 seconds. The hot water shrinkage of the obtained cupra yarn was 1.9%. Using the obtained cupra yarn, the number of frictions until the flat knitted fabric knitted with a single-knitting machine was worn out was 10,250 times. Twist the obtained cupra yarn at 2000 T / m,
This was used as the weft, and a greige machine of crepe desine (warp density 115 / inch, weft density 85 / inch) was prepared using cupra 40d / 24f non-twisted yarn as the warp. Crepe decine having a degree of weft crimp standing orientation of 0.86 was obtained.

Comparative Example 19 Using a cupra yarn (75d / 45f), the number of rubs of a plain knitted fabric knitted by a single-knitting machine until the fabric was worn out was 5,886. The hot water shrinkage of this yarn was measured.
1%. This yarn was twisted at 2,000 T / m, this was used as a weft, and a greige crepe (having a density of 115 yarns / inch and a weft density of 85 yarns / inch) was produced using cupra 75d / 45f non-twisted yarn as the warp yarn. When the crimping was performed according to the formula, the degree of weft crimping orientation was 0.90.
Of crepe decin was obtained.

Comparative Example 2 Using a cupra yarn (40d / 24f), the number of rubs of a plain knitted fabric knitted by a single-knitting machine until it was worn out was 5,500. The hot water shrinkage of this yarn was measured.
2%. This yarn was twisted at 2,000 T / m, this was used as a weft, and a greige crepe (having a density of 115 yarns / inch and a weft density of 85 yarns / inch) was produced using cupra 75d / 45f non-twisted yarn as the warp yarn. When the crimping was performed according to the formula, the degree of weft crimping orientation was 0.90.
Of crepe decin was obtained.

Comparative Example 3 A flat knitted fabric knitted by a single-knitting machine using cupra yarn (75d / 45f) was mixed with 5% by weight of ethylene glycol diglycidyl ether and magnesium borofluoride (acid catalyst).
After immersion in a solution having a composition of 0.6% by weight, magnesium acetate (stabilizer) 0.23% by weight, and water 94.17% by weight, the mixture is squeezed with a mangle (5 kg / cm 2) to 85% by weight with respect to cellulose. And a heat treatment at 130 ° C. for 20 minutes. The number of frictions before the knitted fabric is worn is 512.
Five times. A greige crepe (115 warp / inch, 85 weft / inch) greige machine was prepared using the same yarn as the weft and a cupra 75d / 45f non-twisted yarn as the warp, and crimping was performed by a normal prescription. Thus, crepe decine having a weft crimp standing orientation degree of 0.91 was obtained.

Comparative Example 4 A flat knitted fabric knitted with a single-knitting machine using cupra yarn (40d / 24f) was mixed with 5% by weight of ethylene glycol diglycidyl ether and magnesium borofluoride (acid catalyst).
After immersion in a solution having a composition of 0.6% by weight, magnesium acetate (stabilizer) 0.23% by weight and water 94.17% by weight,
85% by weight of cellulose in mangle (5Kg / cm2)
And heat-treated at 130 ° C. for 20 minutes. The number of times of friction until the knitted fabric was worn out was 5050 times. The same yarn is used as the weft, and the warp as cupra 75
crepe decine (density 11
A greige machine having a density of 5 yarns / inch and a weft density of 85 yarns / inch was prepared and subjected to crimping according to a normal prescription. As a result, crepe decine having a weft crimping orientation of 0.90 was obtained. Table 1 summarizes the above results.

[0023]

[Table 1]

From Table 1, it can be seen that, in Examples 1 to 3 in which specific compounds were applied to undried fibers in the wet spinning method, Comparative Examples 1 and 2 which were not treated with these compounds.
Is excellent in abrasion strength and shrink-proofing property and excellent in embossing property, and excellent in abrasion strength and embossing property in comparison with Comparative Examples 3 and 4 in which these compounds are added after fabricating. Is shown.

[0025]

The artificial cellulose fiber of the present invention has a high abrasion strength and a low hot water shrinkage, and the crepe fabric woven therefrom has excellent crimp standing. Therefore, by using the artificial cellulose fiber of the present invention, it is possible to produce a fabric having a wear strength that can withstand continuous wearing and hardly shrinking by washing or the like. Further, by using the artificial cellulose fiber of the present invention, the conventional resin processing is not required when producing a fiber product, so that the cost can be reduced, and troubles that occur when the resin processing is performed on the fabric. Can be avoided.

Claims (7)

[Claims] 1. An artificial cellulose fiber treated with a compound having two or more functional groups that reacts with cellulose, wherein the number of times of friction until rubbing is 7000 or more and 1 or more.
The hot water shrinkage at 00 ° C. is 2.5% or less, and the crimped fabric using 2,000 T / m twisted yarn of the artificial cellulose fiber as the weft has a crimped orientation degree of 0.87 or less. And artificial cellulose fiber. 2. The artificial cellulose fiber according to claim 1, wherein the compound having two or more functional groups that reacts with cellulose is a compound having a molecular weight of 10,000 or less. 3. The artificial cellulose fiber according to claim 1, wherein the compound having two or more functional groups that reacts with cellulose is an epoxy compound. 4. Cellulose or derivatized cellulose raw material is dissolved and discharged from a spinning port, coagulated and regenerated,
An aqueous dispersion or solution of a compound having two or more functional groups that reacts with cellulose on the undried cellulose fiber after washing with water, when producing an artificial cellulose fiber by a wet spinning method, followed by drying. And then subjecting the mixture to a heat treatment. 5. The artificial cellulose fiber according to claim 4, wherein, in the heat treatment, the evaporation of water and the reaction between the cellulose fiber and a compound having two or more functional groups that react with cellulose are simultaneously performed. Manufacturing method. 6. The method according to claim 4, wherein the compound having two or more functional groups that reacts with cellulose is a compound having a molecular weight of 10,000 or less. 7. The method for producing an artificial cellulose fiber according to claim 4, wherein the compound having two or more functional groups that reacts with cellulose is an epoxy compound.