KR101644067B1 - High-Self Crimping Biodegradable Conjugated Yarn and Process of Producing thereof - Google Patents

Abstract

The present invention relates to a biodegradable composite fiber in which two types of polymers having a large difference in shrinkage from specially designed inclination angle circular nozzles, that is, a first component and a second component polymer, are combined and spin-coated so as to be arranged in a side- And a manufacturing method thereof. According to the present invention, it is possible not only to improve the latent crimping property, but also to produce an excellent touch feeling by being mixed with other materials, and to reduce the manufacturing cost.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biodegradable conjugate fiber,

The present invention relates to a biodegradable conjugate fiber comprising a thermoplastic cellulose derivative and excellent potential winding resistance, and a method for producing the same. Specifically, the present invention relates to a method for producing a biodegradable conjugate fiber excellent in potential winding resistance through a combined spinning process of a thermoplastic cellulose which is excellent in thermal fluidity and capable of melt spinning by using an environmentally friendly plasticizer.

The present invention relates to a biodegradable composite fiber excellent in latent crimping property by using two different biodegradable polymers in combination in a side-by-side cross-sectional shape in the longitudinal direction of the fiber, and a method for producing the same.

As biodegradable polymers, polysaccharides such as cellulose, cellulose derivatives, chitin and chitosan, proteins, aliphatic polyesters such as poly 3-hydroxybutyrate, polyglycolide, polylactic acid and polycaprolactone are known. Of these, cellulose is not only widely available in nature, but also biodegradable under general environmental conditions, and thus has attracted great attention as a typical biodegradable material.

These biodegradable cellulosic fibers are generally produced by wet spinning and dry spinning. However, in wet spinning and dry spinning, it is difficult to obtain a cross-sectional shape of a fiber that conforms to the shape of the nozzle due to the deformation of the polymer during the solidification process of the polymer. Accordingly, it has been difficult to carry out the two kinds of composite spinning, so that it has not been possible to produce fibers having a latent crimp type stretching conventionally.

Korean Patent Laid-Open Publication No. 10-2014-0010742 discloses a technique for producing biodegradable fibers by melt-spinning an environmentally friendly thermoplastic cellulose composition. Specifically, the patent discloses a cellulose composition prepared by adding 10 to 20% by weight of polyethylene glycol, 5 to 15% of poly (lactic acid), and 30 to 50% by weight of a biodegradable polyester copolymer to cellulose acetate. However, the produced cellulose composition of this patent is fibrous but does not exhibit the effect of crimping.

In order to solve the above problems, it is an object of the present invention to provide a biodegradable conjugate fiber having excellent shrinkage potential with the same polymer or two biodegradable polymers having different shrinkage characteristics.

Another object of the present invention is to design a special spinneret and nozzle in which composite spinning of polymers having different viscosity characteristics is possible.

Another object of the present invention is to solve the process defects such as bending and kneeling which are caused by the difference in viscosity between the cellulose derivative and the molecular weight of the cellulose derivative and the content of the plasticizer.

Another object of the present invention is to prepare a latent crimped conjugate fiber having a circular cross section and high crimp performance by controlling the molecular weight of the cellulose derivative and adjusting the amount of the plasticizer to be added.

It is still another object of the present invention to provide a knitted fabric excellent in soft touch, soft gloss and hygroscopicity due to inherent characteristics of cellulosic fibers.

In order to accomplish the above object, the present invention provides a biodegradable composite fiber excellent in potential winding resistance and a method for producing the same, wherein the side-by-side type cellulose-based composite fiber comprises two kinds of polymers having large shrinkage difference , A cellulose-based mixed composition having a viscosity of 500 to 3000 poise as a first component polymer, and a cellulose-based mixed composition having a viscosity of 50 to 1500 poise as a second component polymer, the yarn cross- (Refer to FIG. 4 and FIG. 5). The present invention also provides a method for producing a cellulose-based conjugated fiber excellent in potential crimpability and biodegradability.

&Lt; Equation (1) > 0 < (interface = length of segment CD / length of segment AB) &lt;
&Lt; Equation (2) &gt; 1 (shape = length of segment EF / length of segment GH) 1.4

delete

- Segment AB: Long axis length of interface between high viscosity and low viscosity

- Segment CD: Short axis length of interface between high viscosity and low viscosity / 2

- Segment EF: Maximum length of long axis of yarn section

- Segment GH: Maximum length of the short axis of the yarn section

The present invention also provides a method for producing a biodegradable composite fiber excellent in latent crimping property, wherein the difference in melt viscosity between the first component polymer and the second component polymer during spinning is 2500 poise or less.

The present invention also relates to a method for producing a biodegradable composite fiber, which is characterized in that the first component polymer and the second component polymer are composed of a thermoplastic cellulose mixed composition comprising 70 to 99% by weight of cellulose and 1 to 30% Of the present invention.

The present invention also provides a method for producing a biodegradable conjugate fiber excellent in latent crimping property, characterized in that the cellulose of the cellulose mixture composition has an average degree of substitution in the range of 2.4 to 2.8 and a number average molecular weight of 20,000 to 200,000.

The present invention also relates to a method for producing a polymer electrolyte membrane, wherein the cellulose of the first component polymer and the second component polymer is selected from the group consisting of cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate octanoate, cellulose acetate decanoate Or a combination thereof. The present invention also provides a method for producing a biodegradable conjugate fiber excellent in latent crimping property.

Further, the present invention is characterized in that the plasticizer of the first component polymer and the second component polymer is any one of polyethylene glycol, glycerin, triacetin, epoxidized soybean oil or 1,4-dianhydrosorbitol diester derivative. The present invention also provides a method of producing such an excellent biodegradable composite fiber.

The present invention also provides a method for producing a biodegradable composite fiber excellent in latent crimping property, wherein the cellulose composite fiber has a strength of 1.0 to 3.5 g / denier and an elongation of 20 to 40%.

The present invention also provides a method for producing a biodegradable conjugate fiber having excellent crimpability, wherein the crimp ratio of the cellulose-based conjugate fiber is 10% or more.

The present invention also provides a side-by-side biodegradable composite fiber composed of two polymers having a large difference in shrinkage, wherein the cellulose-based mixed composition having a viscosity of 500-3000 poise as a first component polymer and a cellulose- Wherein the yarn cross-section obtained by composite spinning using a cellulose-based mixed composition of 50 to 1500 poises satisfies the following two expressions and the crimp ratio is 10% or more and the yarn end face satisfies the following two expressions (See Fig. 4 and Fig. 5). The biodegradable conjugate fiber is excellent in potential winding resistance.

&Lt; Equation (1) > 0 < (interface = length of segment CD / length of segment AB) &lt;
&Lt; Equation (2) &gt; 1 (shape = length of segment EF / length of segment GH) 1.4

delete

- Segment AB: Long axis length of interface between high viscosity and low viscosity

- Segment CD: Short axis length of interface between high viscosity and low viscosity / 2

- Segment EF: Maximum length of long axis of yarn section

- Segment GH: Maximum length of the short axis of the yarn section

The biodegradable composite fiber using cellulose according to an embodiment of the present invention can provide the biodegradable fiber excellent in potential winding resistance through the manufacture of side by side melt spinning.

In addition, the present invention is capable of exhibiting an excellent touch feeling by being mixed with other materials, and thus has an advantage that it can be used for spring, summer, and various fashion clothes.

In addition, the present invention has the advantage of reducing the cost of the manufacturing process.

1 is a schematic view of a radiator used in a manufacturing method of the present invention.
2 is a schematic view of a composite spinning pack for use in the present invention.
3 is a schematic view of a conventional circular straight nozzle-type spinning pack.
4 is a schematic view of a section of a yarn of the cellulose-based composite fiber produced by the present invention.
FIG. 5 is a schematic diagram illustrating deformation of a section of a yarn according to manufacturing conditions of the composite fiber produced by the present invention. FIG.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. First, it should be noted that, in the drawings, the same components or parts have the same reference numerals as much as possible. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted so as to avoid obscuring the subject matter of the present invention.

As used herein, the terms "substantially", "substantially", and the like are used herein to refer to a value in or near the numerical value when presenting manufacturing and material tolerances inherent in the meanings mentioned, Absolute numbers are used to prevent unauthorized exploitation by unauthorized intruders of the mentioned disclosure.

Fig. 1 is a schematic view of a radiator used in the manufacturing method of the present invention, Fig. 2 is a schematic view of a composite spinning pack used in the present invention, Fig. 3 is a schematic view of a conventional circular straight nozzle- Fig. 3 is a schematic view of a section of a yarn of the cellulose-based composite fiber produced by the present invention. Fig. 5 is a schematic diagram illustrating deformation of a section of a yarn according to the production conditions of the composite fiber produced by the present invention.

The present invention relates to a biodegradable composite fiber having excellent side-by-side form and latent crimping property composed of two kinds of polymers having large shrinkage difference, and a manufacturing method therefor.

In the present invention, the side-by-side cellulose-based conjugate fiber has a viscosity of 500 to 3,000 poise as a first component polymer (high viscosity) and a cellulose-based mixed composition having a viscosity as a second component polymer (low viscosity) 50 to 1,500 Poise. &Lt; / RTI &gt;

The cellulose mixed composition may be one having a large difference in melt viscosity between the two components (the first component and the second component).

In the process of producing biodegradable fibers according to the present invention, the difference in melt viscosity between the two kinds of polymers is 2500 poise or less.

The cellulose mixed composition may comprise a thermoplastic cellulose mixed composition comprising 70 to 99% by weight of cellulose and 1 to 30% by weight of a plasticizer.

The biodegradable fiber can be produced using the cellulose having an average degree of substitution in the range of 2.4 to 2.8 and a number average molecular weight of 20,000 to 200,000.

The cellulose of the cellulosic mixed composition may be any one of the group consisting of cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate octanoate, and cellulose acetate decanoate, or a combination thereof.

The plasticizer may be any one of polyethylene glycol, glycerin, triacetin, epoxidized soybean oil or a 1,4-dianhydrosorbitol diester derivative, or a combination thereof.

The difference in melt viscosity of the first component polymer and the second component polymer component can be controlled by changing the extruder (1, 1 - 1) temperature condition of each component and varying plasticizer content.

In order to ensure that the difference in melt viscosity between two components during spinning can be maintained in an appropriate region of 500 poise, the spinning temperature of the high viscosity extruder 1 is 260 to 280 ° C, the viscosity of the low viscosity extruder 1-1 The temperature range is preferably adjusted to 240 to 260 ° C.

The melt passing through the extruder can be supplied to one spinning pack 3 while passing through the gear pumps 2, 2-1.

As shown in FIGS. 4 and 5, the cross-section of the yarn irradiated by the difference in melt viscosity forms a circular cross-section, and the interface has a round cross-sectional shape due to the difference in melt viscosity, Is moved within the range satisfying the following formula due to the difference in melt viscosity.

&Lt; Equation (1) > 0 &lt; (interface = length of segment CD / length of segment AB) &lt;

- Segment AB: Long axis length of interface between high viscosity and low viscosity

- Segment CD: Short axis length of interface between high viscosity and low viscosity / 2

The proportion of the high viscosity component in the composite fibers of the cellulose-based mixed composition is preferably 30 to 70% of the total, and the proportion of the low viscosity component in the composite fibers is preferably 70 to 30% of the total.

Also, as each discharge ratio changes, the yarn cross-sectional shape moves within a range satisfying the following expression.

&Lt; Equation (2) > 1 (shape = length of segment EF / length of segment GH) 1.4

- Segment EF: Maximum length of long axis of yarn section

- Segment GH: Maximum length of the short axis of the yarn section

In the present invention, the speed of winding (6) is suitably 1,000 to 4,000 m / min, but is not limited thereto.

 In the spinning step of the composite fibers, the spinning process may be used to spin the yarn.

It is preferable to set the speed of the first godet roller 4 at 500 m / min or more and the speed of the second godet roller 5 at 3,000 m / min or more in the spin draw process to improve the spinning workability and crimp performance .

The drawing temperature of the first godet roller is preferably in the range of 70 to 120 캜. If the stretching temperature is lower than 70 ° C, defective dyeing may occur. If the stretching temperature is higher than 120 ° C, apostrophe is not preferable, which may adversely affect the processability.

The second godet roller preferably has a drawing temperature of about 100 to 160 ° C. If the elongation temperature is lower than 100 ° C, the setting property is poor, and the probability of failure in manufacturing the warp knitted fabric may be high. If the stretching temperature is higher than 160 ° C, the yarn is unstable, have.

The composite fiber of the present invention preferably has a strength of 1.0 to 3.5 g / denier and an elongation of 20 to 40%.

When the strength is less than 1.0 g / denier, the strength is lowered and there are many yarn splices during spinning, the workability of the knitted fabric is poor, and the tear strength of the knitted fabric is lowered. If it exceeds, the tactile sensation after fabrication may be defective.

In the case of shinto, less than 20% is likely to occur during radiation, and if it exceeds 40%, the uniformity (U%) due to apostolic anxiety during the spinning process may become poor.

The composite fibers produced in the present invention preferably have a crimp ratio of 10% or more. If the crimp ratio is 10% or more, it is possible to manufacture a knitted fabric having stretchability characteristics, and if the crimp ratio is less than 10%, the stretch property may be poor when the knitted fabric is manufactured.

Also, when the above formula is satisfied, a large number of crimps per unit length can be expressed through the post-annealing heat treatment process, thereby improving the stretchability of the knitted fabric. In addition, the knitted fabric gives a soft and comfortable fit during manufacture.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

Examples 1 to 8 and Comparative Examples 1 to 4

(A) a cellulose-based composition and (B) a plasticizer in a twin-screw extruder and kneading the mixture at a temperature of 180 ° C to produce a pellet. The resulting pellet is melted through a high viscosity and low viscosity extruder, By spinning the filaments in a side-by-side fashion through a nozzle through a distribution plate in a spin beam, the properties of the filaments were measured. The measurement method of each property is as follows.

* Tensile strength and elongation

The fiber was gripped under a conditioned 20 cm, initial load of 1.0 ± 0.1 cN / tex using an Instron tensile tester under the environment of a temperature of 20 ° C and a humidity of 65%, and a moving clamp was set at a stretching rate of 100% per minute. The strength [g / d] and elongation [%] of the yarn were measured while stretching until the yarn was broken. The number of measurements was 5, and the average value was determined as the strength and elongation.

* Fineness fluctuation value (U%)

And measured by the Wester tester manufactured by Zellweger uster under the following conditions. The number of times of measurement was 5, and the average value was set as U%.

- Measuring speed: 200m / min

- Measurement time: 2.5 minutes

- Measuring fiber length: 500m

- Twist: S twist, 12000 / m

* Shrinkage in boiling water

An initial weight of 50 cm was suspended in a boiling water for 15 minutes, suspended in 200 mg of the sample, dried in the air for 5 minutes, and the shrinkage in boiling water was determined according to the following equation.

Shrinkage (%) = (length of initial sample - length of sample after shrinkage) / length of initial sample × 100

* Cool feeling

The score of 10 points was compared with the score of the sensation of cooling sensation felt when a piece of sacrificed yarn was touched and directly touched.

* Intrinsic Viscosity: Each polymer was dissolved in acetone-ethanol at a concentration of 20%, and then measured using a ball drop viscometer at 25 ° C in a thermostatic chamber.

Crimp rate (Tc,%): Take a sample of the skein of the amount corresponding to 3,000 deniers under the condition that a tension of 50 mg / denier is given to the sample. The sample is treated with hot water (100 ° C) for 20 minutes under a load of 0.5 mg / denier, and then the load is removed and allowed to stand for 24 hours to dry naturally. After the sample is dried naturally, a load of 2 mg / denier is applied to the sample. After a lapse of 1 minute, a length (L1) is measured, and a load of 2 mg / denier + 200 mg / denier is applied. . The measured value is substituted into the following equation (3) to determine the crimp ratio.

&Quot; (3) &quot; Tc (%) = (L2 - L1) / L2 100

* 30% elongation elastic recovery rate of fabric (FR30,%): After making three pieces of 5.5 cm × 30 cm in the weft direction and weft direction, attach the test piece to the tensile tester with a width of 5 cm, . After elongation to 30% elongation at a rate of 100% / min with low elongation measurement method (JSIS L 1018-70), contraction was performed at the same speed in the opposite direction, and the elongation at the stress- (ε) is measured, and the average of each of the light and weft directions is calculated and obtained by the following equation (4).

&Lt; Equation (4) > FR30 (%) = (30 - epsilon) / 30 x 100

* Radioactive evaluation 1

After 7 consecutive days of spinning with melt spinning, the radioactivity was evaluated as A, B and C according to the number of times the cut fibers were generated:

A: 0 times of cutting fiber occurrence for 7 days

B: 1 to 2 times of cutting fiber occurrence for 7 days; And

C: 7 Number of times of cutting fiber occurrence 3 times or more

* Radioactive evaluation 2

When the spin nozzle deteriorates due to the increase of the filtration pressure during 7 consecutive days of spinning, the service life of the spin nozzle is measured by date.

division Example 1
Example 2
Example 3
Example 4
Extruder The that The that The that The that (A) Cellulose Kinds Cellulose acetate Content (wt%) 80 70 80 60 80 70 80 70 (B) a plasticizer Kinds Polyethylene glycol Content (wt%) 20 30 20 40 20 30 20 30 Discharge rate 5 5 5 5 6 4 4 6 Viscosity difference poise 1,980 2,800 2,020 2,200 Process condition Radiation condition m / min 3,000 3,000 3,000 3,000 Radiation temperature ℃ 270 250 272 255 271 251 272 252 Radiation fairness One ◎ △ ◎ ◎ 2 ◎ × ◎ ◎ Yarn characteristics burglar g / De 1.9 1.5 2 2.2 Shindo % 45 35 37 35 Crimp ratio % 55 75 65 70 Variation degree of fineness % 1.5 2.2 1.7 One Shrinkage in boiling water %
6 7 6 7 Knitting / Knitting Characteristics FR30 % 89 91 95 97 Refreshing feeling point 8 7 9 10 Biodegradable point 9 9 9 10

division Example 5 Example 6 Example 7 Example 8 Extruder The that The that The that The that (A) Cellulose Kinds Cellulose acetate Content (wt%) 80 70 80 60 80 70 80 70 (B) a plasticizer Kinds Triacetin Content (wt%) 20 30 20 40 20 30 20 30 Discharge rate 5 5 5 5 6 4 4 6 Viscosity difference poise 2,050 2,900 2,520 2,350 fair
Condition Radiation condition m / min 3,000 3,000 3,000 3,000 Radiation temperature ℃ 271 252 274 252 270 250 274 250 Radiation fairness One ◎ × △ ◎ 2 ◎ △ ◎ ◎ Yarn characteristics burglar g / De 2 1.7 2.1 2.3 Shindo % 47 30 38 37 Crimp ratio % 51 60 61 75 Variation degree of fineness % 1.3 2 1.5 1.1 Shrinkage in boiling water % 7 8 5 8 Knitting / Knitting
characteristic FR30 % 89 91 95 97 Refreshing feeling point 8 7 9
10 Biodegradable point 9 9 9 10

As can be seen in Examples 1 to 8, when the difference in viscosity was 2500 poise or more, the spinning processability was poor due to occurrence of kneeling. However, as the viscosity difference of the high / low viscosity cellulose composition was large, Respectively.

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Extruder The The that that The The The The (A) Cellulose Kinds Cellulose acetate Polyester
Content (wt%) 80 80 80 80 80 80 - - (B) a plasticizer Kinds Dibutyl phthalate - - Content (wt%) 20 20 20 20 20 20 - - Discharge rate 5 5 5 5 6 4 5 5 Viscosity difference poise 100 200 300 1,000 Process condition Radiation condition m / min 3,000 3,000 3,000 4,000 Radiation temperature ℃ 270 270 280 260 271 271 295 295 Radiation fairness One ◎ △ ◎ ◎ 2 ◎ △ ◎ ◎ Yarn characteristics burglar g / De 2 1.9 1.9 3.2 Shindo % 27 28 31 42 Crimp ratio % 2 One 2 2 Variation degree of fineness % 1.1 1.2 1.2 1.2 Shrinkage in boiling water % 4 6 5 7 Knitting / Knitting Characteristics FR30 % 10 12 11 10 Refreshing feeling point 8 8 7 4 Biodegradable point 8 7 8 4

In [Comparative Example 1-4], it was confirmed that even when the polymer having the same shrinkage properties as those in the extruder and the spinning apparatus shown in Fig. there was.

1: Extruder 2: Gear pump
3: Radial pack 4: First godet roller
5: second godet roller 6: winder

Claims (9)

A method for producing a side-by-side type biodegradable fiber comprising two kinds of polymers having large shrinkage difference,
A cellulose-based mixed composition having a viscosity of 500 to 3000 poise as a first component polymer, and a cellulose-based mixed composition having a viscosity of 50 to 1500 poise as a second component polymer, (Refer to FIG. 4 and FIG. 5), which is excellent in latent crimping property.
&Lt; Equation (1) > 0 < (interface = length of segment CD / length of segment AB) &lt;
&Lt; Equation (2) &gt; 1 (shape = length of segment EF / length of segment GH) 1.4
- Segment AB: Long axis length of interface between high viscosity and low viscosity
- Segment CD: Short axis length of interface between high viscosity and low viscosity / 2
- Segment EF: Maximum length of long axis of yarn section
- Segment GH: Maximum length of the short axis of the yarn section The method according to claim 1,
Wherein the difference in melt viscosity between the first component polymer and the second component polymer during spinning is 2500 poise or less. The method according to claim 1,
Wherein the first component polymer and the second component polymer are composed of a thermoplastic cellulose mixed composition comprising 70 to 99% by weight of cellulose and 1 to 30% by weight of a plasticizer. The method according to claim 1,
Wherein the cellulosic mixture composition has an average degree of substitution in the range of 2.4 to 2.8 and a number average molecular weight of 20,000 to 200,000. The method according to claim 1,
Wherein the cellulose of the first component polymer and the second component polymer is any one of the group consisting of cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate octanoate, and cellulose acetate decanoate or a combination thereof By weight based on the total weight of the biodegradable conjugate fiber. The method according to claim 1,
Wherein the plasticizer of the first component polymer and the second component polymer is any one of polyethylene glycol, glycerin, triacetin, epoxidized soybean oil, or 1,4-dianhydrosorbitol diester derivative. The biodegradable A method for producing a composite fiber. The method according to claim 1,
Wherein the cellulose-based composite fiber has a strength of 1.0 to 3.5 g / denier and an elongation of 20 to 40%. The method according to claim 1,
Wherein the crimp ratio of the cellulose-based composite fiber is 10% or more. In a side-by-side type biodegradable conjugate fiber composed of two kinds of polymers having large shrinkage difference,
A cellulose-based mixed composition having a viscosity of 500 to 3000 poise as a first component polymer and a cellulose-based mixed composition having a viscosity of 50 to 1500 poise as a second component polymer are used to produce a composite yarn, A satisfactory composite fiber having a crimp ratio of 10% or more and a cross section of a yarn satisfying the following two formulas (see FIGS. 4 and 5).
&Lt; Equation (1) > 0 < (interface = length of segment CD / length of segment AB) &lt;
&Lt; Equation (2) &gt; 1 (shape = length of segment EF / length of segment GH) 1.4
- Segment AB: Long axis length of interface between high viscosity and low viscosity
- Segment CD: Short axis length of interface between high viscosity and low viscosity / 2
- Segment EF: Maximum length of long axis of yarn section
- Segment GH: Maximum length of the short axis of the yarn section

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