KR20160082179A - The composite of thermaplastic cellulose ester dope dyed yarn, thermaplastic cellulose ester dope dyed yarn and Manufacturing method thereof - Google Patents

Abstract

The present invention relates to a thermoplastic cellulose ester dope dyed yarn composition, a thermoplastic cellulose ester dope dyed yarn manufactured by using the same, and a manufacturing method for the same and, more particularly, to a thermoplastic cellulose ester dope dyed yarn composition, a thermoplastic cellulose ester dope dyed yarn manufactured by using the same, and a manufacturing method for the same in which a cellulose ester resin derived from pulp with a particular property is employed for significant improvement in melt spinning property and manufacturing of a high-productivity dope dyed yarn with excellence in mechanical property and dyeability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic cellulose ester homopolymer, a thermoplastic cellulose ester homopolymer, a thermoplastic cellulose ester homopolymer, a thermoplastic cellulose ester homopolymer, a thermoplastic cellulose ester homopolymer,

TECHNICAL FIELD The present invention relates to a thermoplastic cellulose ester homogenous fiber composition, a thermoplastic cellulose ester homogeneous fiber, and a process for producing the same. More specifically, the present invention relates to a thermoplastic cellulose ester homogeneous fiber composition, The present invention relates to an invention capable of producing an originally formed fiber having excellent dyeability with high productivity.

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 ester resin comprising a mixture of a thermoplastic cellulose derivative and a plasticizer, which is a cellulose ester 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 is not caused by melting under the melt spinning temperature due to strong hydrogen bonding between the molecular chains of the cellulose ester 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.

In addition, cellulose ester fibers are not easy to dye, so dyeing with a uniform color tone requires a great deal of skill, and high temperatures are required under certain pressures in order for the cellulose ester fibers to absorb the high energy disperse dye. Since the processing process using white polyester yarn involves complicated steps, there are disadvantages such as an increase in manufacturing cost, an increase in the processing cost of the salt wastewater by a separate dyeing process, and an environmental problem caused by the wastewater have.

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

Disclosure of the Invention The present invention has been conceived to solve the problems as described above. It is an object of the present invention to provide a cellulose ester resin derived from a specific pulp in order to maximize compatibility between a cellulose ester resin and a colored dye, Thermoplastic cellulose ester-bonded fibers having excellent physical properties, excellent color purity and light fastness, and high productivity by performing melt spinning with a chip prepared by mixing the dyes, and a method for producing the thermoplastic cellulose ester- Composition.

The present invention relates to a melt-spinning thermoplastic cellulosic ester based fiber composition comprising a cellulose ester resin, a plasticizer, a radical formation inhibitor, a radical activity inhibitor and a color pigment, wherein the cellulose ester resin satisfies the following equation 1 and the following equation 2 And the like.

[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, the thermoplastic cellulose ester based adhesive fiber composition of the present invention comprises 25 to 45 parts by weight of a plasticizer, 0.01 to 2 parts by weight of a radical generation inhibitor, 0.01 to 2 parts by weight of the radical activity inhibitor 0.01 To 2.5 parts by weight of a coloring pigment and 1 to 5 parts by weight of a coloring pigment.

As a preferred embodiment of the present invention, in the composition of the present invention, the cellulose ester resin preferably 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, a melting temperature of 230 to 250 ° C . ≪ / RTI >

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

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

As a preferred embodiment of the present invention, in the composition of the present invention, the cellulose ester resin is dispersed in a CAB solution according to the Pt-Co standard, and then has a color of 220 to 350 ppm when measured and measured according to ASTM D871 And a haze of 35 to 50 ppm in the measurement.

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

In a preferred embodiment of the present invention, in the composition of the present invention, the color pigment is a carbon black having an average particle diameter of 10 nm to 1,000 nm.

In a preferred embodiment of the present invention, in the composition of the present invention, the cellulose ester 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 succinate, cellulose acetate laurethate, cellulose acetate palmitate, cellulose acetate stearate, and cellulose acetate oleate.

As a preferred embodiment of the present invention, in the composition of the present invention, the plasticizer is selected from the group consisting of polyethylene glycol having a weight average molecular weight of 350 to 750, polypropylene glycol, polyglycolic acid, polybutyl adipate, glycerin, tributyl sebacate, And at least one selected from the group consisting of citrate and triethyl citrate.

As a preferred embodiment of the present invention, in the composition of the present invention, the radical generation inhibitor includes a water insoluble compound including a phenol group, and the radical activity inhibitor includes a water insoluble compound containing phosphorus at the terminal thereof .

In a preferred embodiment of the present invention, in the composition 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 selected from the group consisting of: Or more species.

As a preferred embodiment of the present invention, in the composition of the present invention, the radical activity inhibitor is selected from the group consisting of tris (2,4-di-t-butylphenyl) phosphite and tris Or more species.

As a preferred embodiment of the present invention, the thermoplastic cellulose ester based adhesive fiber composition of the present invention has a melt viscosity of 90.0 to 150.0 Pa.sec and a heat flow of 70 to 130 g, measured at 260 캜 according to ASTM D1238, / 10 minutes, and a shear rate of 130 to 170 / s.

Another object of the present invention is to provide a method for producing a thermoplastic cellulose ester conjugate fiber, comprising the steps of: preparing a mixture by mixing various types of thermoplastic cellulose ester conjugate fiber compositions as described above; Adding the mixture 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 chip through a spinneret to produce a thermoplastic cellulose ester bond fiber.

In one preferred embodiment of the present invention, the blending is performed under a condition that the internal temperature of the kneader is increased from 150 ° C to 220 ° C.

As a preferred embodiment of the present invention, in the manufacturing method of the present invention, the kneader is a kneader equipped with a twin-screw extruder, and the blending is performed by a circulator feeder at 20 to 30 kg / hr and a kneader at a motor speed of 220 to 300 rpm And the like.

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 265 to 290 ° C.

Another object of the present invention is to provide a method for producing an oriented fiber having an average fineness of 50 to 200 d and a strength of 0.7 g / de to 1.8 g / de as measured according to the KS K 0412 method, 18% to 30%.

According to one preferred embodiment of the present invention, the thermoplastic cellulose ester conjugate fiber of the present invention has a light fastness of 3 when the light fastness of the knitted fabric is measured by XENON-ARC-LAMP, BLUE SCALE according to the KS K ISO 105 method, Or more.

A cellulose ester resin derived from a specific pulp is introduced in order to maximize the compatibility of a cellulose ester resin and a coloring dye to produce an original fiber, whereby the cellulose ester resin is excellent in mechanical properties such as strength and elongation, It is possible to produce a thermoplastic cellulose ester conjugate fiber with high productivity and economy because it has good melt viscosity, heat flowability and transmission rate and excellent melt spinnability, And a thermoplastic cellulose ester-bonded fiber excellent in all-round fastness can be provided.

Hereinafter, the present invention will be described in detail.

The present invention relates to a thermoplastic cellulose ester-bonded fiber produced by using a cellulose ester resin synthesized from a specific pulp in order to improve the compatibility between the melt spinning and cellulose ester resin of the present invention and a colored dye.

The composition used in the production of the thermoplastic cellulose ester base fiber of the present invention includes a cellulose ester resin, a plasticizer, a radical formation inhibitor, a radical activity inhibitor and a coloring pigment.

In the present invention, the cellulose ester resin is produced by synthesizing a stretch having specific physical properties. The pulp is a pulp satisfying the following Equation 1 and the following Equation 2, preferably the following Equation 1-1 and Equation 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 in the cellulose ester 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. When the degree of substitution of the cellulose ester resin is less than 2.0, the fluidity of the molecules is lowered when the cellulose ester resin is melted, so that the melt processability may be deteriorated. In the case where the degree of substitution of the cellulose ester resin is 2.8 , Not only the biodegradability is lowered but also the problem that the melt emitter cellulose ester resin is carbonized at a high temperature may occur.

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.

The cellulose ester 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. If the weight average molecular weight is less than 35,000, the length of the cellulose main chain is short, If the weight average molecular weight exceeds 55,000, the penetration of the plasticizer is not easy and there may be a problem that the flowability of the cellulose molecules in the melt extrusion process may decrease. Therefore, the weight average molecular weight within the above range Is preferably used.

The cellulose ester resin has a melting temperature of 230 ° C to 250 ° C and a glass transition temperature of 185 ° C to 195 ° C, preferably 187 ° C to 192 ° C, which is excellent in heat resistance and can be melt-spun at a high temperature.

The water content of the cellulose ester resin is 2 to 4% by weight, preferably 2.5 to 3.5% by weight based on the total weight of the resin.

The cellulose ester resin has a viscosity of 100 poise to 130 poise, preferably 105 poise to 120 poise, more preferably 110 poise to 120 poise, as measured according to ASTM D1343. Conventionally, the cellulose ester resin used for melt spinning has a viscosity of 10 poise to 60 poise, but the cellulose ester resin synthesized from the specific pulp of the present invention has 100 to 130 poise, which can greatly improve the high temperature melt spinnability at high temperatures .

The cellulose ester resin is dispersed in a CAB solution according to the Pt-Co standard and has a color of 220 ppm to 350 ppm, preferably 250 to 320 ppm, more preferably 270 ppm to 310 ppm, 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.

The cellulose ester resin preferably 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 , more preferably 420 kg / m ³ to 438 kg / m ³ . The cellulose ester resin may have a bulk bulk density of 300 kg / m ³ to 340 kg / m ³ , preferably 310 kg / m ³ to 330 kg / m ³ .

The plasticizer, which is one of the thermoplastic cellulose ester bondable fiber compositions of the present invention, is not particularly limited as long as it is mixed with a cellulose ester resin to prevent strong hydrogen bonding due to hydroxyl groups present in the cellulose resin and to allow melt spinning, Average molecular weight of 350 to 750, preferably 400 to 650 so as to promote plasticization. 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 25 to 45 parts by weight, preferably 27 to 42 parts by weight, more preferably 28 to 35 parts by weight, based on 100 parts by weight of the cellulose ester resin, and less than 25 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.

The thermoplastic cellulosic ester based fiber composition of the present invention includes a radical formation inhibitor and a radical activity inhibitor. The radical generation inhibitor is used when thermoplasticity of the cellulose ester resin or after plasticizing the plasticized cellulose ester resin is preliminarily melted , It plays a role of preventing decomposition by heat and suppresses the generation of radicals generated by the chain, so that 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 amount of the radical generation inhibitor may be 0.01 to 2 parts by weight, preferably 0.05 to 1.0 part by weight, based on 100 parts by weight of the cellulose resin. When the amount is less than 0.01 part by weight, The cellulose resin may be thermally decomposed in the course of thermoplasticization or spinning. If it exceeds 2 parts by weight, there may be a problem in workability as a cause of an increase in pack pressure.

In addition, the thermoplastic cellulose ester originally bonded fiber composition of the present invention can provide a fused yarn, that is, a yarn having a low defective ratio and excellent physical properties, by using not only a radical generation inhibitor but also a radical activity inhibitor. 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 activity inhibitor may be used in an amount of 0.01 to 2.5 parts by weight, preferably 0.05 to 1.5 parts by weight, based on 100 parts by weight of the cellulose ester resin. If the amount is less than 0.01 part by weight, the ability to prevent thermal decomposition during melting may be insufficient and the cellulose ester resin melted in the thermoplastic or melt spinning process may be thermally decomposed. If the amount exceeds 2.5 parts by weight, .

In the thermoplastic cellulose ester bondable fiber composition of the present invention, the coloring pigment may contain a coloring aid component other than carbon black, but the blending ratio of carbon black to the whole coloring pigment is preferably 30 wt% or more. The average particle diameter of carbon black is preferably 10 nm to 1,000 nm, more preferably, carbon black having an average particle diameter of 50 nm to 700 nm. At this time, if the average particle diameter of the carbon black exceeds 1,000 nm, the pack pressure of the spinning portion rises and yarn breakage occurs, resulting in a decrease in radioactivity and carbon black to be separated from the fibers may occur. Phthalocyanine blue having a substitution degree of chlorine atom of 1, phthalocyanine blue pigment, etc. may be used as the coloring aid component, but it is not limited to any one.

In addition, in the thermoplastic cellulose ester based adhesive fiber composition of the present invention, the amount of the color pigment to be used may be 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, based on 100 parts by weight of the cellulose resin. If the compounding ratio of the color pigment is less than 0.5, the content of the coloring pigment may be too low to exhibit the performance of the original sheet. If the amount is 5 parts by weight or more, uniform resin is hardly produced during melt extrusion. It is preferable to use the above-mentioned blending ratio.

When the melt flow index is measured at 260 ° C according to the ASTM D1238 method, the mixed resin obtained by mixing the thermoplastic cellulose ester starting fiber composition of the present invention having the composition and composition ratio has a melt viscosity of 90.0 Pa.sec to 150.0 Pa.sec , Preferably from 95.0 Pa.sec to 140 Pa.sec.

The melt-cellulose ester resin of the present invention has a heat flow rate of 70 g / 10 min to 130 g / 10 min and a shear rate of 130 (g / 10 min) when measured according to the ASTM D1238 method, / s ~ 170 / s.

Hereinafter, a method for producing the thermoplastic cellulose ester conjugate fiber of the present invention using the thermoplastic cellulose ester based adhesive fiber composition will be described.

The method for producing a thermoplastic cellulose ester bondable fiber of the present invention comprises the steps of: preparing a mixture by mixing a thermoplastic cellulose ester bond fiber composition; Adding the mixture 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 chip through a spinneret to produce a thermoplastic cellulose ester bond fiber.

A plasticizer, a radical formation inhibitor, a radical activity inhibitor, and a coloring dye, and the characteristics of these compositions, the amounts used, and the like are the same as those described above.

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 carried out under the condition of raising the temperature from 150 ° C to 220 ° C, preferably from 160 ° C to 210 ° 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 220 ° 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 temperature range.

The blending is preferably carried out at 20 to 30 kg / hr of the circle feeder and at 220 to 300 rpm of the kneader, preferably at 22 to 28 kg / hr of the circle feeder and 240 to 290 rpm of the kneader The resin is smoothly kneaded and 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.

It is preferable that the melt spinning is carried out at a spinning speed of 2,000 to 3,000 mpm and a spinning temperature of 255 to 280 DEG C, preferably at a spinning speed of 2,200 to 2,900 mpm and at a spinning temperature of 260 to 275 DEG C. More preferably, A speed of 2,300 to 2,800 mpm and a spinning temperature of 265 ° C to 275 ° 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 high, which is not suitable for the spinning operation. Therefore, there may be a problem in the yarn splicing in the nozzle, and if the spinning temperature exceeds 280 캜, There may be a problem that the resin is thermally decomposed to cause discoloration of color or physical properties and 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 in various shapes such as a cross-shaped cross-section, a polygonal cross-section, a C-shaped cross-section, a circular cross-section, a cross-section cross-section, For example, a 36-hole round cross-section can be used.

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.

The thermoplastic cellulose ester conjugate fiber of the present invention prepared through the above composition and the production method may have a fineness of 50 to 200 denier when measured according to the KS K ISO 2060 method and preferably 100 to 150 denier . The thermoplastic cellulose ester-bonded fiber has a strength of 0.7 g / de to 1.8 g / de, preferably a fiber strength of 0.7 g / de to 1.5 g / de, more preferably a strength Can be from 0.8 g / de to 1.3 g / de. In addition, the elongation may have an elongation of 15% or more, preferably 18% to 30%, and more preferably 18% to 26%.

In addition, the thermoplastic cellulose ester conjugate fiber of the present invention may have a light fastness of 3 or more in the light fastness of the knitted fabric when measuring light fastness by standard dimming of XENON-ARC-LAMP and BLUE SCALE according to the KS K ISO 105 method, 4 or higher.

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

A 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 pulverized using cellulose acetate having a cellulose degree of substitution of 2.4, a weight average molecular weight of 40,000 and a melting temperature of 242 캜 using a general cellulose acetate synthesis method Acetate resin. 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 Example of comparison preparation
One Example of comparison preparation
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: Molten cellulose ester Of extruded fibers  Produce

(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) 0.1 part by weight of tris (2,4-di-t-butylphenyl) phosphate (Alcanox 240, Camtura Corporation) as a radical activity inhibitor and 2 parts by weight of carbon black (average particle diameter 350 nm) , And then mixed with a supermixer for 10 minutes to prepare a resin-like mixture.

Next, the mixture was fixed at 25 kg / hr of a circle feeder and at 270 rpm of a kneader using a kneader equipped with a twin-screw extruder, and then kneaded at a kneader die (DIE) And blended for 5 minutes while applying a temperature of up to 240 DEG C 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) Thermoplastic Cellulose Ester Of extruded fibers  Produce

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-bonded fiber having a fineness of 120 denier.

Example  2

A thermoplastic cellulose ester-bonded fiber 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 a L / D of 1.5 of a circular cross-section spinneret was used.

Example  3

A thermoplastic cellulose ester conjugate fiber 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 = 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 To produce an original fiber.

Example  5

The same procedure as in Example 1 was carried out except that 35 parts by weight of polyethylene glycol as a plasticizer was used to prepare a thermoplastic cellulose ester-bonded fiber having a fineness of 120 denier in the same manner as in Example 1. [

Example  6

The same procedure as in Example 1 was carried out except that 25 parts by weight of polyethylene glycol as a plasticizer was used in the same manner as in Example 1 to prepare a thermoplastic cellulose ester bonding fiber having a fineness of 120 denier.

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 in the same manner as in Example 1, to prepare thermoplastic cellulose ester-bonded fibers having a fineness of 120 denier.

Example  8

The procedure of Example 1 was repeated except that 1 part by weight of carbon black was used to prepare a thermoplastic cellulose ester bonding fiber having a fineness of 120 denier in the same manner.

Comparative Example  One

A thermoplastic cellulose ester-bonded fiber 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 a L / D of 0.9 of a circular-section spinneret was used.

Comparative Example  2

Except that the temperature at the nozzle portion of the spinneret was 285 ° C, a thermoplastic cellulose ester-bonded fiber having a fineness of 120 denier was prepared in the same manner as in Example 1

Comparative Example  3

The same procedure as in Example 1 was carried out except that the temperature at the nozzle portion of the spinneret was 250 ° C to prepare a thermoplastic cellulose ester bonding fiber having a fineness of 120 denier.

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 bonded fiber 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-bonded fiber having a fineness of 120 denier was prepared in the same manner.

Comparative Example  6

The same procedure as in Example 1 was carried out except that 15 parts by weight of polyethylene glycol as a plasticizer was used to prepare a thermoplastic cellulose ester conjugate fiber having a fineness of 120 denier in the same manner as in Example 1. [

Comparative Example  7

The same procedure as in Example 1 was carried out except that 50 parts by weight of polyethylene glycol as a plasticizer was used to prepare a thermoplastic cellulose ester conjugate fiber having a fineness of 120 denier in the same manner as in Example 1.

Comparative Example  8

Except that polyethylene glycol having a weight average molecular weight of 200 instead of polyethylene glycol having a weight average molecular weight of 600 was used as a plasticizer in the same manner as in Example 1 except that the polyethylene glycol having a weight average molecular weight of 200 was used.

Comparative Example  9

Except that polyethylene glycol having a weight average molecular weight of 1000 was used instead of polyethylene glycol having a weight average molecular weight of 600 as a plasticizer, a thermoplastic cellulose ester-bonded fiber having a fineness of 120 denier was prepared.

Comparative Example  10

The same procedure as in Example 1 was carried out except that 7 parts by weight of carbon black was used to prepare a thermoplastic cellulose ester conjugate fiber having a fineness of 120 denier.

Experimental Example  1: Measurement of physical properties of cellulose ester composition

The melt temperature, melt viscosity, heat flow and shear rate of the mixed resin, which is a mixture of the melt-cellulose ester compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 10, were measured at 260 占 폚 according to the ASTM D1238 method, The results are shown in Table 2 below.

division Melting point
(Pa.sec) Heat flowability
(g / 10 min) Shear rate
(S ^-1 ) Example 1 123.7 86.3 154.8 Example 2 123.7 86.3 154.8 Example 3 123.7 86.3 154.8 Example 4 114.8 98.7 159.1 Example 5 113.5 101.9 162.2 Example 6 150.1 74.9 133.5 Example 7 121.5 91.1 157.3 Example 8 130.1 83.4 156.6 Comparative Example 1 123.7 86.3 154.8 Comparative Example 2 123.7 86.3 154.8 Comparative Example 3 123.7 86.3 154.8 Comparative Example 4 Not measurable Comparative Example 5 53.4 145.6 194.3 Comparative Example 6 164.6 62.6 101.4 Comparative Example 7 53.5 142.5 267.3 Comparative Example 8 35.1 177.8 292.2 Comparative Example 9 Not measurable Comparative Example 10 120.4 90.3 159.4

Experimental Example  2: melt cellulose ester chips and Of extruded fibers  Property measurement

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 8 and Comparative Examples 1 to 10 The results are shown in Table 3 below.

(1) 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. Indicates that the melt spinning is very good, & cir & indicates that the melt spinning is good, & cir & indicates that the yarn is defective upon melt spinning, and x indicates that melt spinning is impossible.

(2) 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 grip 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 constant force, and the value (%) of the initial length as a percentage of the elongated length Respectively.

(3) Light fastness  Measure

According to KS K ISO 105 method, the light fastness of thermoplastic cellulose ester fiber knitted fabric was measured by standard dimming of XENON-ARC-LAMP and BLUE SCALE.

As a result of the test results shown in Table 3, in the case of Examples 1 to 8, extrusion workability and radiation workability were generally excellent. However, in Comparative Examples 1 to 10, the spinning workability was relatively poor as compared with the Examples.

In the case of Comparative Example 5 in which cellulose acetate resin 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 used, the strength and elongation In addition, the results of the measurement of the fastness to light were not good, which is attributed to the difference in the material and physical properties of the cellulose acetate resin itself.

Through the above Examples and Experimental Examples, it is confirmed that the cellulose ester resin of the present invention has a high melting temperature and an optimal melt viscosity, heat flow and shear rate which can be melt-spun at a high temperature of 260 ° C as a biodegradable resin I could. In the present invention, not only the melt spinnability is improved by introducing the cellulose ester resin, but also the compatibility with the coloring dye is maximized to prepare the melted cellulose ester chip and the thermoplastic cellulose ester conjugate fiber, and their color (b ^* ) And it was confirmed that it is excellent. Further, it was confirmed that the present invention not only provides a yarn having excellent extrusion workability and radiation workability, but also excellent strength and elongation, as well as excellent yarn fastness and light fastness.

Claims (17)

A cellulose ester resin, a plasticizer, a radical formation inhibitor, a radical activity inhibitor and a coloring pigment,
Wherein the cellulose ester resin is 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%.
The cellulose ester resin according to claim 1, wherein the cellulose ester resin
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% Wherein the thermoplastic cellulose ester-bonded fiber composition is a thermoplastic resin.
The cellulose ester resin according to claim 1, wherein the cellulose ester resin has a viscosity of 100 to 130 poise when measured according to ASTM D1343, dispersed in a CAB solution according to a Pt-Co standard, 350 ppm, and a haze of 35 ppm to 50 ppm as measured according to ASTM D871.
2. The method of claim 1, wherein the cellulose ester resin has a tapped bulk density of 410 kg / m ³ to 450 kg / m ³ and a poured bulk density of 300 kg / m ³ to 340 kg / / m < ³ >, based on the total weight of the thermoplastic cellulose ester.
The composition of claim 1, further comprising 25 to 45 parts by weight of a plasticizer, 0.01 to 2 parts by weight of a radical generation inhibitor, 0.01 to 2.5 parts by weight of the radical activity inhibitor, and 0.5 to 5 parts by weight of a color pigment, based on 100 parts by weight of the cellulose ester resin Based on the weight of the thermoplastic cellulose ester.
The thermoplastic resin composition according to claim 5, wherein the colored pigment is carbon black having an average particle diameter of 10 nm to 1,000 nm.
The cellulose ester resin composition according to claim 5, wherein the cellulose ester resin
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 A thermoplastic cellulose ester-based fiber composition comprising at least one thermoplastic cellulose ester-based fiber composition.
The method of claim 5, wherein the plasticizer
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 cellulose ester-based fiber composition.
The method of claim 5, wherein the radical generation inhibitor is tetrakis (methylene) (3,5-di-t-butyl- Butyl-4-hydroxyphenyl) propionate and tetrakis methylene (3,5-di-t-butyl-4-hydroxyphenyl) propionate methane. A cellulose ester-based fiber composition.
The thermoplastic resin composition according to claim 5, 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 cellulose ester-based fiber composition.
The composition according to any one of claims 1 to 10, wherein the composition has a melt viscosity of 90.0 Pa.sec to 150.0 Pa.sec and a heat flow of 70 g / 10 minutes to 130 g / 10 minutes, and a shear rate of 130 / s to 170 / s.
Mixing the thermoplastic cellulosic ester based adhesive fiber composition of claim 11 to produce a mixture;
Adding the mixture 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;
Wherein the thermoplastic cellulose ester-bonded fiber comprises a thermoplastic resin.
13. The method according to claim 12, wherein the blending is performed under a condition of raising the internal temperature of the kneader from 150 DEG C to 220 DEG C.
13. The method of claim 12, wherein the detachment is a circular sectioned detonator and the length / depth (L / D) ratio of the detente length to the detente depth is 1.0 to 4.0.
The method of claim 12, wherein the melt spinning is performed at a spinning speed of 2,000 to 3,000 mpm and a spinning temperature of 255 to 280 ° C.
A composition comprising the composition of claim 11 and having an average fineness of from 50 to 200 d and a strength of from 0.7 g / de to 1.8 g / de and an elongation of from 18% to 30% as measured according to the method of KS K 0412 Original fiber.
16. The thermoplastic cellulose ester conjugate fiber according to claim 15, wherein the light fastness of the knitted fabric is at least grade 3 when measured by light fastness by XENON-ARC-LAMP or BLUE SCALE according to the KS K ISO 105 method.