KR20160079298A - Thermaplastic cellulose ester yarn, and Manufacturing method thereof - Google Patents

Abstract

The present invention relates to a thermoplastic cellulose ester yarn and a method of manufacturing thereof, and more specifically, to an invention introducing a cellulose-based resin derived from a specific pulp, thereby greatly improving melt-spinning properties to allow yarn having excellent physical properties to be produced with high productivity.

Description

TECHNICAL FIELD The present invention relates to a thermoplastic cellulose ester yarn,

TECHNICAL FIELD The present invention relates to a thermoplastic cellulose ester yarn and a method for producing the same, and more particularly, to a method for producing a thermoplastic cellulose ester yarn by introducing a cellulose resin derived from a pulp having a specific physical property into a yarn .

Polymer synthetic resins have been extensively used for a variety of purposes because of their excellent mechanical properties, chemical resistance and durability. However, such synthetic resins have a disadvantage in that harmful substances are released when they are incinerated because they are not decomposed by themselves in nature. Recently, environmental pollution problem has become a big social problem, and biodegradable resins that can be completely decomposed in nature have been actively studied and are attracting interest worldwide.

Although biodegradable resins such as polybutylene succinate, polyethylene succinate and polylactic acid are excellent in biodegradability, they are not economical due to their high cost, or have a low melting point, In the manufacture of products such as textile products, it is difficult to develop a product group that needs to maintain thermal stability.

Recently, products such as polylactic acid (PLA) or starch have been spotlighted in recent biomass-based products, which are supplied from nature. However, they can not be dyed at high temperature for fiberization and are susceptible to hydrolysis, When the tenter work is carried out, it has various disadvantages such as hardening and brittle characteristic.

Cellulosic materials are biodegradable resource-recycling biomass materials that can be produced in pulp and are therefore produced in the largest amount on the earth without the need for separate cultivated land and water. The use of cellulose as a fiber has been conventionally carried out by spinning short fibers such as cotton and hemp produced in the natural environment. In order to obtain a filament material other than short fibers, cellulose is dissolved in a specific solvent to effect wet spinning, cellulose is derivatized such as cellulose acetate, dissolved in an organic solvent such as methylene chloride or acetone, A dry spinning process has been carried out with evaporation (Korean National Publication No. KR 2002-0080821). However, these wet spinning or dry spinning fibers have a problem of low productivity due to a low spinning speed, and also have problems in that the organic chemicals such as disulfide carbon, acetone, and methylene chloride used in the production of fibers have a bad influence on the environment It is difficult to say that it is environmentally friendly fiber because it is worried about going crazy. For this reason, in order to obtain an environmentally-bottomed low-profile fiber comprising cellulose as a raw material, it is necessary to use a melt spinning method that does not use an organic agent

Conventional thermoplastic cellulose derivatives can be produced by melt extruding a low molecular weight phthalate plasticizer into a sheet or by using an injection process after chip production to apply to a handle of a tool such as a screwdriver, Respectively. However, since the conventional thermoplastic cellulosic derivatives have a problem of poor workability due to plasticizer volatilization and other large amounts of gas generated in the chip during melt spinning, the properties of the yarn are remarkable due to the thermal stability of the melted resin and the lack of viscosity. .

For example, U.S. Pat. No. 2,030,066 discloses a cellulose-based resin comprising a mixture of a thermoplastic cellulose derivative and a plasticizer, which is a cellulose-based resin for the purpose of producing a calendared sheet, The workability is poor due to the lack of viscosity, and there is a problem that it is difficult to form fibers by melt spinning. That is, there is a problem that carbonization occurs without melting under the melt spinning temperature due to strong hydrogen bonding between the molecular chains of the cellulose resin.

In addition, China Patent No. 100381622 discloses a technique for a thermoplastic cellulose derivative composition comprising, as a main component, a cellulose ester having an aliphatic polyester side chain having a repeating unit of 2 to 5 carbon atoms, which uses an expensive cellulose derivative , There is a problem that the production cost is too high and the economical efficiency and the commerciality are greatly deteriorated.

China Patent No. 100381622 (Published on Apr. 16, 2008)

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the above problems, and it is an object of the present invention to provide a cellulose ester resin derived from a specific pulp and melt- A thermoplastic cellulose ester yarn having productivity and a method for producing the same.

The present invention relates to a melt-spinning thermoplastic cellulose ester yarn, characterized by comprising a cellulose resin derived from a pulp satisfying the following Equation (1) and Equation (2).

[Equation 1]

95.0 wt%? A? 99.5 wt%

In the above equation (1), A represents the weight of a residue in an aqueous NaOH solution after stirring and dissolving a pulp having a weight average molecular weight of 10,000 g / mol or less in a 10 vol% NaOH aqueous solution at 25 캜 for 1 hour %to be.

[Equation 2]

0.5%? B? 3.5%

In the above equation (2), B represents the concentration of a soluble substance in an aqueous NaOH solution measured after stirring and dissolving a pulp having a weight average molecular weight of 10,000 g / mol or less in an aqueous NaOH solution of 18% by volume concentration at 25 캜 for 1 hour Weight%.

As a preferred embodiment of the present invention, in the thermoplastic cellulose ester yarn of the present invention, the cellulose resin has a degree of substitution of cellulose hydroxyl groups of 2.0 to 2.8, a weight average molecular weight of 35,000 to 55,000, Lt; RTI ID = 0.0 > 250 C. < / RTI >

In a preferred embodiment of the present invention, in the thermoplastic cellulose ester yarn of the present invention, the cellulose resin has a glass transition temperature of 185 ° C to 195 ° C and a water content of 2% by weight to 4% by weight .

As a preferred embodiment of the present invention, in the thermoplastic cellulose ester yarn of the present invention, the cellulose resin may have a viscosity of 100 to 130 poise when measured according to ASTM D1343.

In a preferred embodiment of the present invention, in the thermoplastic cellulose ester yarn of the present invention, the cellulose resin has a color of 220 to 350 ppm when measured after dispersed in a CAB solution according to the Pt-Co standard, And a haze of 35 to 50 ppm when measured according to ASTM D871.

In a preferred embodiment of the present invention, in the thermoplastic cellulose ester yarn of the present invention, the cellulose based resin has a bulk bulk density of 410 to 450 kg / m ³ and a bulk bulk density, Is 300 to 340 kg / m < ³ >.

As a preferred embodiment of the present invention, the thermoplastic cellulose ester raw material of the present invention has an average fineness of 30 to 200 de and has a strength of 0.5 to 2.0 g / de and an elongation of 20 to 35% measured according to the method of KS K 0412 .

Another object of the present invention is to provide a method for producing the thermoplastic cellulose ester yarn as described above, comprising the steps of: preparing a molten cellulose ester resin; Adding the molten cellulose ester resin to a kneader, and performing blending to produce a molten cellulose ester chip; Drying the molten cellulose ester chip at 70 ° C to 90 ° C for 20 to 30 hours; And melt spinning the dried molten cellulose ester chips through a spinneret to produce a thermoplastic cellulose ester yarn.

In one preferred embodiment of the present invention, the molten cellulose ester resin in the step of producing a molten cellulose ester resin is a resin composition containing 20 to 45 parts by weight of the plasticizer, 0.01 to 1.5 parts by weight of the radical generation inhibitor per 100 parts by weight of the cellulose- And 0.01 to 2 parts by weight of the radical activity inhibitor.

As a preferred embodiment of the present invention, the cellulose resin may be produced by synthesizing pulp satisfying the following Equation (1) and Equation (2).

[Equation 1]

95.0 wt%? A? 99.5 wt%

In the above equation (1), A represents the weight of a residue in an aqueous NaOH solution after stirring and dissolving a pulp having a weight average molecular weight of 10,000 g / mol or less in a 10 vol% NaOH aqueous solution at 25 캜 for 1 hour %to be.

[Equation 2]

0.5%? B? 3.5%

In the above equation (2), B represents the concentration of a soluble substance in an aqueous NaOH solution measured after stirring and dissolving a pulp having a weight average molecular weight of 10,000 g / mol or less in an aqueous NaOH solution of 18% by volume concentration at 25 캜 for 1 hour Weight%.

In one preferred embodiment of the present invention, in the production method of the present invention, the cellulose resin is selected from the group consisting of cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate caproate, cellulose acetate caprylate , Cellulose acetate laurethate, cellulose acetate palmitate, cellulose acetate stearate, and cellulose acetate oleate.

As a preferred embodiment of the present invention, in the production method of the present invention, the plasticizer has a weight average molecular weight of 350 to 750, and the plasticizer is selected from the group consisting of polyethylene glycol, polypropylene glycol, polyglycolic acid, polybutyl adipate, glycerin, Butyl sebacate, triacetin, and triethyl citrate. ≪ Desc / Clms Page number 7 >

As a preferred embodiment of the present invention, in the production method of the present invention, the radical generation inhibitor comprises a water-insoluble compound including a phenol group, and the radical activity inhibitor comprises a water- . ≪ / RTI >

As a preferred embodiment of the present invention, in the production method of the present invention, the radical generation inhibitor is at least one selected from the group consisting of tetrakis methylene (3,5-di-t-butyl-4-hydroxycinnamate) methane, pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propionate methane, and 3- And may include one or more species.

In a preferred embodiment of the present invention, the radical activity inhibitor is selected from the group consisting of tris (2,4-di-t-butylphenyl) phosphite and tris-nonylphenyl phosphite and triphenylphosphite And may include one or more species.

As a preferred embodiment of the present invention, in the production method of the present invention, the melt-cellulose ester resin may have a melt viscosity of 95.0 to 160.0 Pa.sec when measured at 260 캜 according to the ASTM D1238 method have.

As a preferred embodiment of the present invention, in the production method of the present invention, the melt-cellulose ester resin has a heat flow rate of 60 g / 10 min to 120 g / 10 min when measured at 260 ° C under the ASTM D1238 method , And a shear rate of 120 / s to 160 / s.

In one preferred embodiment of the present invention, the blending is performed under the condition that the internal temperature of the kneader is raised from 150 ° C to 240 ° C.

As a preferred embodiment of the present invention, in the production method of the present invention, the kneader is a kneader equipped with a twin-screw extruder, and the blending is performed at 20 kg / hr to 30 kg / hr of a circle feeder and at 220 rpm To 300 rpm.

According to a preferred embodiment of the present invention, in the manufacturing method of the present invention, the crotch is a circular cross section, and the circular cross section has a length / depth (L / D) .

As a preferred embodiment of the present invention, in the production method of the present invention, the melt spinning may be performed at a spinning speed of 2,000 mpm to 3,000 mpm and a spinning temperature of 255 to 275 ° C.

The present invention relates to a thermoplastic cellulose ester yarn produced by introducing a specific cellulose-based resin synthesized from a specific pulp, which is excellent in physical properties such as strength and elongation, and the specific cellulose resin and / The cellulose resin, which is one of the main components, is not carbonized and can have an appropriate melt viscosity, heat flow rate, and transmission rate even at a high temperature. As a result, the thermoplastic cellulose ester yarn Can be manufactured.

Hereinafter, the present invention will be described in detail.

The present invention relates to a thermoplastic cellulose ester yarn produced by using a cellulose resin synthesized from a specific pulp to improve the melt spinnability of the present invention.

In the present invention, the cellulose resin is produced by synthesizing a pulp having specific physical properties. The pulp is preferably a pulp satisfying the following Equation 1 and the following Equation 2, preferably the following Equation 1-1 and the following equation Pulp satisfying 2-1 can be used.

[Equation 1]

95.0 wt%? A? 99.5 wt%

[Equation 1-1]

97.5 wt% < / = A < / = 99.0 wt%

In the above-mentioned Equation 1 and Equation 1-1, A is a pulp having a weight average molecular weight of 10,000 g / mol or less, preferably 8,000 g / mol or less pulp at 25 ° C for 1 hour Is the weight percent of the residue in the aqueous NaOH solution after stirring and dissolving.

 [Equation 2]

0.5%? B? 3.5%

[Equation 2-1]

1.0%? B? 2.5%

In the above-mentioned Equation 2 and Equation 2-1, B is a pulp having a weight average molecular weight of 10,000 g / mol or less and preferably 8,000 g / mol or less pulp at a concentration of 18 vol% NaOH aqueous solution at 25 캜 for 1 hour Is the weight percentage of the soluble substance in the NaOH aqueous solution measured after stirring and dissolving.

The degree of substitution of the cellulose hydroxyl group of the cellulose resin is 2.0 to 2.8, preferably the degree of substitution is 2.2 to 2.7, and more preferably the degree of substitution is 2.3 to 2.5. The substitution degree of the cellulose-based resin means the degree of substitution of the hydroxyl group of the cellulose by the ester bond. When the degree of substitution of the cellulose-based resin is less than 2.0, the fluidity of the molecules may be lowered during melting, , The biodegradability is deteriorated, and the melt-spinning machine cellulose-based resin may be carbonized at a high temperature.

The cellulose resin may be selected from the group consisting of cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate caproate, cellulose acetate caprylate, cellulose acetate laurethate, cellulose acetate palmitate, cellulose acetate stearate, Cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate and cellulose acetate caprate, and preferably one or more selected from among cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate and cellulose acetate caprate Or more, and more preferably, cellulose acetate, cellulose acetate As propionate and cellulose may include one or more kinds selected from the group consisting of acetate butyrate.

In the present invention, the cellulose resin preferably has a weight average molecular weight of 35,000 to 55,000, preferably a weight average molecular weight of 35,000 to 45,000. When the weight average molecular weight is less than 35,000, the cellulose main chain The mechanical properties of the yarn may be reduced. If the weight average molecular weight is more than 55,000, penetration of the plasticizer may not be easy and there may be a problem that the fluidity of the cellulose molecules in the melt extrusion process may decrease. Therefore, It is preferable to use one having a weight average molecular weight in the range of

The cellulose-based resin used in the present invention has a melting temperature of 230 to 250 占 폚 and a glass transition temperature of 185 to 195 占 폚, preferably 187 to 192 占 폚. It is excellent in heat resistance, Is possible.

The cellulose-based resin used in the present invention has a moisture content of 2 to 4% by weight, preferably 2.5 to 3.5% by weight, based on the total weight of the resin.

In addition, the cellulose resin used in the present invention has a viscosity of 100 to 130 poise, preferably 105 to 120 poise, and more preferably 110 to 120 poise, as measured according to ASTM D1343. Conventionally, the cellulose resin used for melt blowing has a viscosity of 10 to 60 poise, but the cellulose resin synthesized from the specific pulp of the present invention has 100 to 130 poise, which can greatly improve the high temperature melt radiation at high temperature.

The cellulose resin used in the present invention is dispersed in the CAB solution according to the Pt-Co standard and has a color of 220 to 350 ppm, preferably 250 to 320 ppm, more preferably 270 To 310 ppm. The cellulose resin has a haze of 35 ppm to 50 ppm, preferably 35 ppm to 45 ppm, and more preferably 37 ppm to 45 ppm, as measured according to ASTM D871. There is a characteristic that the purity is superior to the cellulose derivative.

In addition, the cellulose-based resin used in the present invention has a tapped bulk density of 410 kg / m ³ to 450 kg / m ³ , preferably 410 kg / m ³ to 440 kg / m ³ , And preferably from 420 kg / m ³ to 438 kg / m ³ . The cellulosic resin may have a pore bulk density of 300 kg / m ³ to 340 kg / m ³ , preferably 310 kg / m ³ to 330 kg / m ³ .

The thermoplastic cellulose ester raw material thus produced may have a fineness of 30 to 200 denier, preferably 70 to 150 denier when measured according to the KS K ISO 2060 method. The thermoplastic cellulose ester raw material preferably has a strength of 0.5 to 2.0 g / d, preferably 0.6 to 1.8 g / d, more preferably 0.7 to 1.5 g / d, as measured according to the KS K 0412 method. lt; / RTI > In addition, the elongation may have an elongation of 20% or more, preferably 20% to 35%, and more preferably 22% to 32%.

Hereinafter, a method for producing the thermoplastic cellulose ester yarn of the present invention having such characteristics will be described.

The thermoplastic cellulose ester source of the present invention comprises the steps of: preparing a molten cellulose ester resin; Adding the molten cellulose ester resin to a kneader, and performing blending to produce a molten cellulose ester chip; And drying the molten cellulose ester chips at 70 ° C to 90 ° C for 20 to 30 hours; And melt spinning the dried molten cellulose ester chip through a spinneret.

The molten cellulose ester resin in the step of preparing the molten cellulose ester resin includes a cellulose resin, a plasticizer, a radical formation inhibitor and a radical activity inhibitor.

The cellulosic resin of the above-mentioned molten cellulose ester resin is the same as that described above.

The plasticizer, which is one of the components of the molten cellulose ester resin, is not particularly limited as long as it is mixed with the cellulose resin to inhibit strong hydrogen bonding due to the hydroxyl groups present in the cellulose resin and to allow melt spinning. It is preferable to use a compound having a weight average molecular weight of 350 to 750, preferably 400 to 650 so as to accelerate the polymerization. If the weight average molecular weight of the plasticizer is less than 350, the plasticizer may dissolve out of the resin during melt spinning and volatilize. If the weight average molecular weight exceeds 750, penetration into the cellulose main chain is not easy, There may be a problem of decrease.

Such plasticizers include phthalic esters such as dimethyl phthalate, diethyl phthalate, dihexyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate, ethyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate; Aromatic polycarboxylic acid esters such as tetraoctyl pyromellitate and trioctyl trimellitate; Aromatic polycarboxylic acid esters such as dibutyl adipate, dioctyl adipate, dibutyl sebacate, dioctyl sebacate, diethyl azelate, dibutyl azelate and dioctyl azelate; Lower fatty acid esters of polyhydric alcohols such as glycerin triacetate, diglycerin tetraacetate and polyglycolic acid; Phosphoric acid esters such as triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate and tricresyl phosphate; Aliphatic polyesters composed of glycols and dibasic acids such as polyethylene glycol, polypropylene glycol, polyethylene adipate, polybutylene adipate, polyethylene succinate, and polybutylene succinate; Aliphatic polyesters composed of oxycarboxylic acids such as polyglycolic acid; Aliphatic polyesters composed of lactones such as polycaprolactone, polypropiolactone, and polar valerolactone; Vinyl polymers such as polyvinylpyrrolidone; Tributyl sebacate; Triacetin; And triethyl citrate; , And the like. More preferably, one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polyglycolic acid, polybutyl adipate, glycerin, tributyl sebacate, triacetin and triethyl citrate can be used.

The amount of the plasticizer to be used is preferably 20 to 45 parts by weight, preferably 22 to 40 parts by weight, more preferably 25 to 35 parts by weight, based on 100 parts by weight of the cellulose resin, and less than 20 parts by weight Thermal treatment may not be possible due to insufficient thermoplasticization of the cellulose resin during use, and if it is used in excess of 45 parts by weight, there may be a problem of fuming during melt spinning, mechanical properties of the fiber may be deteriorated due to excessive plasticization, There may be a problem that the plasticizer breed-out occurs on the surface of the melt sprayed by melt-spinning.

In addition, the molten cellulose ester resin includes a radical generation inhibitor and a radical activity inhibitor. When the cellulose-based resin is thermolabelled or the plasticized cellulose-based resin is chipped and melted before spinning, the radical- And prevents the generation of radicals generated in the chain. Thus, it is possible to spin at high temperature and to provide a molten radiator having excellent physical properties. The radical generation inhibitor may be in the form of a liquid or solid phase which can be easily mixed with the cellulose resin and the plasticizer, preferably a water-insoluble compound containing a phenol group, more preferably tetrakis methylene (3,5 Di-t-butyl-4-hydroxycinnamate) methane, pentaerythritol tetrakis (3- (3,5- And 5-di-t-butyl-4-hydroxyphenyl) propionate methane. Specific examples thereof include Anox 20 (Chemtura Co.), Iganox 1010 (Ciba Specialty Chemicals, Inc ) And Songnox 1010 (Songwon International Co., Ltd.).

The radical generation inhibitor may be used in an amount of 0.01 to 1.5 parts by weight, preferably 0.05 to 1.0 part by weight, based on 100 parts by weight of the cellulose resin. If the amount is less than 0.01 part by weight, The cellulose resin may be thermally decomposed in the course of thermo-digestion or spinning. If it exceeds 1.5 parts by weight, there may be a problem in workability as a cause of an increase in pack pressure.

In the present invention, by using not only a radical generation inhibitor but also a radical activity inhibitor, the above-mentioned molten cellulose ester resin can provide a fused yarn, that is, a yarn having a low defective rate and excellent physical properties. In the present invention, the radical generation inhibitor plays a role in preventing oxidation of the melt-spun yarn in the atmosphere and inhibits the generation of radicals generated by breaking of the cellulose main chain. The radical activity inhibitor may be in the form of a liquid or solid phase which can be easily mixed with a cellulose resin and a plasticizer, and preferably a water-insoluble compound containing phosphorus at the terminal may be used. More preferably, the tris (2,4- Di-t-butylphenyl) phosphite, and tris-nonylphenyl phosphite and triphenyl phosphite. Specific examples thereof include Alkanox 240 (Chemtura Co.), Igafos 168 (manufactured by Ciba Specialty Chemicals , Inc., and Songnox 1680 (Songwon Industrial Co., Ltd.).

The radical scavenging agent may be used in an amount of 0.01 to 2.0 parts by weight, preferably 0.03 to 1.2 parts by weight, based on 100 parts by weight of the cellulose resin. If the amount is less than 0.01 part by weight, The cellulose based resin melted in the thermoplastic or melt spinning process may be thermally decomposed. If the amount exceeds 2.0 parts by weight, there may be a problem in workability and moldability as a cause of increase in pack pressure.

The melt-cellulose ester resin of the present invention having such a composition and composition ratio has a melt viscosity of 95.0 Pa.sec to 160.0 Pa.sec, preferably 95.0 Pa.sec To 140 Pa.sec.

In addition, the melt-cellulose ester resin of the present invention has a heat flow rate of 60 g / 10 min to 120 g / 10 min and a shear rate of 120 / s to 160 / min when measured according to ASTM D1238, s.

Next, the step of producing a molten cellulose ester chip will be described.

The blending of the step of producing a molten cellulose ester chip in the production method of the present invention is preferably carried out under the condition of raising the temperature from 150 ° C to 240 ° C, preferably 160 ° C to 230 ° C, If the internal temperature of the kneader is less than 150 ° C, the resin may not sufficiently melt and the resin may not be smoothly kneaded and may be released in an unmelted state If the temperature is higher than 240 ° C, the main chain of the cellulose ester may be thermally decomposed due to excessive heat, resulting in a problem in that the color of the chip may be browned to deteriorate the physical properties. Therefore, blending is preferably performed in the above temperature range.

The blending is preferably carried out at a speed of 20 kg / hr to 30 kg / hr of the circle feeder and at a speed of 220 rpm to 300 rpm of the kneader, preferably 22 kg / hr to 28 kg / hr of the circle feeder, Performing the kneading at a speed of 240 rpm to 290 rpm results in smooth kneading of the resin, which is advantageous in view of stable workability and productivity.

The kneader may be a general kneader used in the art, preferably a kneader equipped with a twin-screw extruder.

The drying of the molten cellulose ester chips is carried out at 70 ° C to 100 ° C for 20 to 30 hours, preferably at 75 ° C to 85 ° C for 20 to 26 hours, more preferably at 78 ° C to 85 ° C If the drying temperature is less than 70 ° C., the drying time may become too long, resulting in a decrease in commerciality. In addition, if the drying temperature exceeds 100 ° C., Heat may impart fluidity to the polymer chain, and thermal deformation and thermal decomposition may occur in the chip.

Next, the step of melt-spinning will be described.

More preferably, the melt spinning is carried out at a spinning speed of 2,000 mpm to 3,000 mpm and a spinning temperature of 255 to 275 ° C, preferably at a spinning speed of 2,200 to 2,900 mpm and a spinning temperature of 255 to 270 ° C, Is preferably carried out at a spinning rate of 2,300 to 2,800 mpm and a spinning temperature of 260 to 270 ° C. If the spinning speed is less than 2,000 mpm, the productivity may be reduced and the production cost may increase. If the spinning speed exceeds 3,000 mpm, the tensile force or the blow-out phenomenon may occur due to too high tension applied to the molten cellulose yarn. So that it is preferable to perform melt spinning under the above-mentioned spinning speed. If the spinning temperature is less than 255 캜, the melt viscosity of the melted cellulose resin is too high to be suitable for spinning, which may cause a problem in yarn splicing in the nozzle. If the spinning temperature exceeds 275 캜, There may be a problem that the resin is thermally decomposed to discolor the color, the physical properties thereof deteriorate, and the melt radiation property is poor.

And, the detachment used for the melt spinning can be a conventional detachment used in the art, and preferably a detachment section detachment can be used. In addition, the above-mentioned shaped cross-section can be used as a cross-shaped cross-section having various shapes such as a cross-section cross-section, a polygonal cross-section, a C-cross-section, a circular cross-section, a cross-section cross-section,

When the above-mentioned circular sectioned section is used, it is preferable to use a circular sectioned section having a length / depth (L / D) ratio between the length of the section and the depth of the opening of 1.0 to 4.0, preferably 1.4 to 3.6 It is recommended to use a circular cross-section with a 2.0 ~ 3.0 cross section. If the L / D value is less than 1.0, there may be a problem that the back pressure applied to the cuff is too low to increase the uniformity of the yarn. If the L / D value exceeds 4.0, There is a problem that the flow of the resin is not smooth and the physical properties of the yarn may be reduced. Therefore, it is preferable to use a circular cross-section cutter satisfying the L / D value.

Hereinafter, the present invention will be described more specifically by way of examples. However, the following examples should not be construed as limiting the scope of the present invention, but should be construed to facilitate understanding of the present invention.

[ Example ]

Preparation Example  1: Preparation of cellulose acetate resin

Pulp having an A value of 98.0% by weight in the following equation (1) and a B value of 2.0% by weight in the following equation (2) was changed to a cellulose acetate having a substitution degree of 2.4, a weight average molecular weight of 40,000 and a melting temperature of 242 Lt; 0 > C. The other properties of the cellulose acetate resin are shown in Table 1 below.

[Equation 1]

95.0 wt%? A? 99.5 wt%

In the above Equation 1, A represents the weight of a residue in an aqueous NaOH solution measured after stirring and dissolving a pulp having a weight average molecular weight of 8,000 g / mol or less in a 10 vol% NaOH aqueous solution at 25 캜 for 1 hour %to be.

[Equation 2]

0.5%? B? 3.5%

In the above equation (2), B represents the concentration of a soluble substance in an aqueous NaOH solution measured after stirring and dissolving a pulp having a weight average molecular weight of 8,000 g / mol or less at a concentration of 18% by volume in an aqueous NaOH solution at 25 캜 for 1 hour Weight%.

Preparation Example  2

A pulp having an A value of 95.2 wt% and a B value of 3.3 wt% of the equation (2) was synthesized in the same manner as in Preparation Example 1 to prepare a cellulose acetate resin.

Example of comparison preparation  One

A pulp having an A value of 93.1% by weight in Equation 1 and a B value of 4.5% by weight in Equation 2 was synthesized in the same manner as in Preparation Example 1 to prepare a cellulose acetate resin.

Example of comparison preparation  2

A cellulose acetate resin (trade name: Eastman Chemical, trade name CA-398-10) having a cellulose substitution degree of 2.4 and a weight average molecular weight of 40,000, which had been conventionally used in the production of molten cellulose ester yarn, was prepared and physical properties thereof are shown in Table 1 below.

division Preparation Example 1 Preparation Example 2 Comparative Preparation Example 1 Comparative Preparation Example 2 pulp Residue content
(in 10 vol% NaOH) 98.0
weight% 95.2
weight% 93.1
weight% - Soluble matter content
(in 10 vol% NaOH) 2.0
weight% 3.3
weight% 4.5
weight% - cellulose
acetate
Suzy cellulose
Degree of substitution 2.4 2.4 2.4 2.4 Weight average molecular weight 40,000 40,000 40,000 40,000 Melting temperature (캜) 242 245 251 240 Glass transition temperature (캜) 189 192 205 180 Water content (% by weight) 3 3.2 3.1 3.5 Viscosity (poise) 114 105 87 38 Color (Color, ppm) 290 225 109 80 Haze (ppm) 40 37 26 25

Example  1: Manufacture of melt-cellulose ester yarn

(1) Production of molten cellulose ester chips

100 parts by weight of the cellulose acetate resin prepared in Preparation Example 1 was mixed with 30 parts by weight of polyethylene glycol (polyethylene glycol) having a weight average molecular weight of 600 as a plasticizer to prepare a mixture.

Next, 100 parts by weight of the mixture was mixed with tetrakis methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane (Anox 20 (Chemtura Corporation) And 0.4 parts by weight of tris (2,4-di-t-butylphenyl) phosphate (Alcanox 240, Camtura Corporation) as a radical activity inhibitor were added to the mixture, and the mixture was stirred for 10 minutes using a supermixer To prepare a melted cellulose ester resin.

Next, the molten cellulose ester resin was fixed at 25 kg / hr of a circle feeder and 270 rpm of a kneader using a kneader equipped with a twin-screw extruder, and then kneaded at five stages of kneader die (DIE) And blended for 5 minutes while applying a temperature to a final terminal temperature of 240 캜 to prepare a molten cellulose ester chip.

Next, the molten cellulose ester chips were dried at 80 DEG C for 24 hours to prepare dried molten cellulose ester chips.

(2) Production of thermoplastic cellulose ester yarn

The dried melt-cellulose ester chip was spin-coated at a spinning speed of 2,500 mpm, a spinning temperature (and a nozzle temperature) of 260 ° C, and a spinning speed of 200 rpm, to a melt spinning machine equipped with a 36- And a discharge rate of 30.0 g / min to prepare a thermoplastic cellulose ester yarn having a fineness of 120 denier.

Example  2

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1, except that a 36-hole round-section spinneret having an L / D of 1.5 of a circular-section spinneret was used.

Example  3

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1, except that a 36-hole circular cross-section spinneret having an L / D of 3.5 of a circular cross-section spinneret was used.

Example  4

Except that the cellulose acetate resin prepared in Preparative Example 2 was used instead of the cellulose acetate resin prepared in Preparation Example 1 to obtain a thermoplastic cellulose ester having a fineness of 120 denier Yarn was produced.

Example  5

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1, except that 35 parts by weight of polyethylene glycol as a plasticizer was used.

Example  6

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1, except that 22 parts by weight of polyethylene glycol as a plasticizer was used.

Example  7

Except that polyethylene glycol having a weight average molecular weight of 400 was used instead of polyethylene glycol having a weight average molecular weight of 600 as a plasticizer, a thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared.

Comparative Example  One

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1, except that a 36-hole circular cross-section spinneret having L / D = 0.9 of a circular cross-section spinneret was used.

Comparative Example  2

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1, except that the nozzle temperature of the spinneret was 280 ° C

Comparative Example  3

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1, except that the temperature at the nozzle of the spinneret was 250 ° C.

Comparative Example  4

The procedure of Example 1 was repeated except that the cellulose acetate resin prepared in Comparative Preparation Example 1 was used instead of the cellulose acetate resin prepared in Preparation Example 1, A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared.

Comparative Example  5

The procedure of Example 1 was repeated except that the conventional cellulose acetate resin of Comparative Preparation Example 2 was used instead of the cellulose acetate resin prepared in Preparation Example 1, A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner.

Comparative Example  6

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1, except that 15 parts by weight of polyethylene glycol as a plasticizer was used.

Comparative Example  7

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1, except that 50 parts by weight of polyethylene glycol as a plasticizer was used.

Comparative Example  8

A thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared in the same manner as in Example 1 except that polyethylene glycol having a weight average molecular weight of 200 was used instead of polyethylene glycol having a weight average molecular weight of 600 as a plasticizer.

Comparative Example  9

Except that polyethylene glycol having a weight average molecular weight of 1,000 was used instead of polyethylene glycol having a weight average molecular weight of 600 as a plasticizer, a thermoplastic cellulose ester yarn having a fineness of 120 denier was prepared.

Experimental Example  1: Melting Cellulose ester  Measurement of physical properties of resin

The melt temperature, melt viscosity, heat flow and shear rate of the melt-cellulose ester resin prepared in Examples 1 to 7 and Comparative Examples 1 to 9 were measured at 260 ° C according to ASTM D1238, Respectively.

division Melting point
(Pa.sec) Heat flowability
(g / 10 min) Shear rate
(S ^-1 ) Example 1 133.1 81.6 147.2 Example 2 133.1 81.6 147.2 Example 3 133.1 81.6 147.2 Example 4 125.6 86.9 151.4 Example 5 97.2 107.9 159.3 Example 6 155.3 69.9 121.6 Example 7 128.4 91.6 154.9 Comparative Example 1 133.1 81.6 147.2 Comparative Example 2 133.1 81.6 147.2 Comparative Example 3 133.1 81.6 147.2 Comparative Example 4 27.3 220.4 312.8 Comparative Example 5 57.6 135.2 184.3 Comparative Example 6 176.9 51.6 91.8 Comparative Example 7 43.5 152.2 287.1 Comparative Example 8 38.2 167.5 302.9 Comparative Example 9 Not measurable

Experimental Example  2: Measurement of physical properties of melted cellulose ester chips and yarns

The extrusion workability, the spinning workability, the color of the chips, the color of the yarn, the strength of the yarn, the elongation of the yarn, and the occurrence time of yarn yarns were measured in the same manner as in Examples 1 to 7 and Comparative Examples 1 to 9 The results are shown in Table 3 below.

(1) Melting Cellulose ester  Color measurement of chips and yarns

B), index ASTM E313-73, color difference equation? E * ab (CIE 1976), and color difference? E * b? ΔE * 94 (CIE1994) and brightness, saturation, and hue.

The measured b ^* values are shown in Table 3 below.

At this time, if the b ^* value of the chip exceeds 5, the main chain of cellulose is cut off due to excessive heat at the time of extrusion, and carbonization occurs. When b ^* value is close to 0, the color is excellent and there is almost no pyrolysis and excellent workability .

When the b ^* value of the yarn exceeds 8, the cellulose resin is carbonized by heat and browned, and when the b ^* value is closer to 0, the color is better, which is advantageous for coloring the dye upon dyeing.

(2) Extrusion workability and radiation workability

In the following Table 3, " & cir & indicates excellent extrusion, & cir & indicates good extrusion, &Dgr; indicates extrusion Indicates that the extrusion is impossible, and X indicates that extrusion is impossible.

The spinning workability was evaluated by judging threading occurrence, gas generation, static electricity generation, winding state, etc. in passing through the melt spinning process under the above-described conditions and judging whether the cellulose resin was melt-processed and capable of high-speed spinning. In Table 3, Indicates that the melt spinning is very good, & cir & indicates that the melt spinning is good, & cir & indicates that the yarn is broken due to the melt spinning, and x indicates that melt spinning is impossible.

(3) Strength and elongation of yarn

The strength and elongation of the fibers were measured using an automatic tensile tester (Textechno) at a speed of 50 cm / m and a gripping distance of 50 cm. The strength and elongation are determined by dividing the load (d) by the denier when the fiber is stretched until it is cut by a given force, and the value (%) of the initial length as a percentage of the elongated length Respectively.

The properties of the yarns prepared in Examples 1 to 7 of the present invention are shown in Table 3. The yarns of Examples 1 to 7 are excellent in extrusion workability and spinning workability and have a chip color of less than 4.40 and a yarn color of 7.5 or less And it was confirmed that it has excellent dye coloring property.

On the contrary, in the case of Comparative Example 1 in which the ratio of length to depth of penetration (length / depth, L / D) of less than 1.0 was used in spinning using a circular cross-section, there was a problem of poor spinning workability, Comparative Example 2 in which the spinning temperature (nozzle temperature) was 280 ° C and Comparative Example 3 in which the spinning temperature (nozzle temperature) was 250 ° C also had poor spinning workability and had a problem of yarn breakage. As a result, , The strength and elongation of the yarn were adversely affected.

Also, the cellulose acetate resin prepared in pulp having an A value of 93.1 wt% in Equation 1 and a B value of 4.5 wt% in Equation 2 had low melt viscosity, high heat flow and shear rate, In the case of Comparative Example 4, not only extrusion workability but also radiation workability were not very good.

Comparative Example 5, which used cellulose acetate resin conventionally used in the related art, was excellent in extrusion workability and spinning workability. However, as compared with Example 1, the dyeability of chips and yarn was poor , And the strength and elongation of the yarn were decreased.

In Comparative Example 6 in which the plasticizer was used in an amount of less than 20 parts by weight, there was a problem that the spinning workability was inferior. In Comparative Example 7 where the plasticizer was used in an amount exceeding 45 parts by weight, the strength and elongation And there was a problem that bleeding out of the plasticizer occurred.

In the case of Comparative Example 8 using polyethylene glycol having a weight average molecular weight of less than 350, there was a problem that the strength and elongation of the yarn were greatly lowered as compared with Example 1. In Comparative Example 9 using polyethylene glycol having a weight average molecular weight of 1,000 , There is a problem that it is difficult to manufacture a yarn because the compression and spinning workability is not so good.

Through the above Examples and Experimental Examples, the melt-cellulose ester resin of the present invention is a biodegradable resin which has a high melting temperature and has an optimum melt viscosity, heat flow property and shear rate which can be melt-radiated at a high temperature of 260 ° C I could confirm. It was confirmed that the color (b ^* ) of the melt-cellulose ester chip prepared using the melt-cellulose ester resin of the present invention was excellent. Further, it was confirmed that the melt-cellulose ester resin and / or chip of the present invention can provide a yarn having excellent extrusion workability and radiation workability, and excellent strength and elongation.

Claims (17)

A cellulose resin derived from a pulp satisfying the following equation (1) and the following equation (2): < EMI ID = 1.0 >
[Equation 1]
95.0 wt%? A? 99.5 wt%
In the above equation (1), A represents the weight of a residue in an aqueous NaOH solution after stirring and dissolving a pulp having a weight average molecular weight of 10,000 g / mol or less in a 10 vol% NaOH aqueous solution at 25 캜 for 1 hour %to be.
[Equation 2]
0.5%? B? 3.5%
In the above equation (2), B represents the concentration of a soluble substance in an aqueous NaOH solution measured after stirring and dissolving a pulp having a weight average molecular weight of 10,000 g / mol or less in an aqueous NaOH solution of 18% by volume concentration at 25 캜 for 1 hour Weight%.
The cellulose-based resin composition according to claim 2, wherein the cellulose-
A degree of substitution of cellulose hydroxyl groups of 2.0 to 2.8, a weight average molecular weight of 35,000 to 55,000, a melting temperature of 230 ° C to 250 ° C, a glass transition temperature of 185 ° C to 195 ° C and a moisture content of 2 to 4% ≪ / RTI >
The thermoplastic cellulose ester yarn according to claim 1, wherein the cellulose resin has a viscosity of 100 to 130 poise when measured according to ASTM D1343.
The cellulose resin according to claim 1, wherein the cellulose resin has a color of 220 to 350 ppm when measured after dispersing in a CAB solution according to a Pt-Co standard, and has a haze of 35 (measured by ASTM D871) To 50 ppm. ≪ / RTI >
The thermoplastic cellulose ester yarn according to claim 1, wherein the average fineness is 30 to 200 de and the strength is 0.5 to 2.0 g / de and the elongation is 20 to 35% as measured according to the KS K 0412 method.
Preparing a molten cellulose ester resin;
Adding the molten cellulose ester resin to a kneader, and performing blending to produce a molten cellulose ester chip;
Drying the molten cellulose ester chip at 70 ° C to 90 ° C for 20 to 30 hours; And
Melt spinning the dried molten cellulose ester chips through a spinneret;
≪ RTI ID = 0.0 > 1, < / RTI >
7. The method of claim 6, wherein the fused cellulose ester resin comprises 20 to 45 parts by weight of a plasticizer, 0.01 to 1.5 parts by weight of a radical generation inhibitor, and 0.01 to 2 parts by weight of a radical activity inhibitor, based on 100 parts by weight of the cellulose-
Wherein the cellulose-based resin is produced by synthesizing a pulp satisfying the following Equation 1 and Equation 2: < EMI ID = 1.0 >
[Equation 1]
95.0 wt%? A? 99.5 wt%
In the above equation (1), A represents the weight of a residue in an aqueous NaOH solution after stirring and dissolving a pulp having a weight average molecular weight of 10,000 g / mol or less in a 10 vol% NaOH aqueous solution at 25 캜 for 1 hour %to be.
[Equation 2]
0.5%? B? 3.5%
In the above equation (2), B represents the concentration of a soluble substance in an aqueous NaOH solution measured after stirring and dissolving a pulp having a weight average molecular weight of 10,000 g / mol or less in an aqueous NaOH solution of 18% by volume concentration at 25 캜 for 1 hour Weight%.
[Claim 8] The method according to claim 7, wherein the cellulose-
Selected from cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate caprate, cellulose acetate caprylate, cellulose acetate laurethate, cellulose acetate palmitate, cellulose acetate stearate and cellulose acetate oleate Wherein the thermoplastic cellulose ester yarn comprises at least one kind of thermoplastic cellulose ester yarn.
The method of claim 7, wherein the plasticizer comprises
Characterized in that it comprises at least one selected from polyethylene glycol having a weight average molecular weight of 350 to 750, polypropylene glycol, polyglycolic acid, polybutyl adipate, glycerin, tributyl sebacate, triacetin and triethyl citrate. A method for producing a cellulose ester yarn.
The method according to claim 7, wherein the radical generation inhibitor comprises a water insoluble compound including a phenol group, and the radical activity inhibitor comprises a water insoluble compound containing phosphorus at the terminal. The method for producing a thermoplastic cellulose ester yarn .
The method of claim 10, wherein the radical generation inhibitor is selected from the group consisting of tetrakis methylene (3,5-di-t-butyl-4-hydroxycinnamate) methane, pentaerythritol tetrakis (3- (3,5- Butyl-4-hydroxyphenyl) propionate and tetrakis methylene (3,5-di-t-butyl-4-hydroxyphenyl) propionate methane. A method for producing a cellulose ester yarn.
11. The composition of claim 10 wherein the radical activity inhibitor comprises at least one selected from tris (2,4-di-t-butylphenyl) phosphite and tris-nonylphenyl phosphite and triphenyl phosphite. A method for producing a cellulose ester yarn.
The method for producing a thermoplastic cellulose ester yarn according to claim 6, wherein the melt-cellulose ester resin has a melt viscosity of 95.0 to 160.0 Pa.sec when measured at 260 캜 according to ASTM D1238.
The method for producing a thermoplastic cellulose ester yarn according to claim 6, wherein the thermofusible cellulose ester yarn has a heat flow rate of 60 to 120 g / 10 min and a shear rate of 120 to 160 / s as measured according to ASTM D1238 at 260 캜 .
7. The method according to claim 6, wherein the blending is performed under a condition of raising the internal temperature of the kneader from 150 DEG C to 240 DEG C.
7. The method of claim 6, wherein the detachment has a circular cross section and the length / depth (L / D) ratio is between 1.0 and 4.0.
The method according to claim 6, wherein the melt spinning is performed at a spinning speed of 2,000 mpm to 3,000 mpm and a spinning temperature of 255 ° C to 275 ° C.