KR20160080666A

KR20160080666A - Excellent dyeing textile of cellulose blended yarn and Dyeing method thereof

Info

Publication number: KR20160080666A
Application number: KR1020140193347A
Authority: KR
Inventors: 임지영; 손정아; 오영일; 임성수
Original assignee: 도레이케미칼 주식회사
Priority date: 2014-12-30
Filing date: 2014-12-30
Publication date: 2016-07-08

Abstract

The present invention relates to a fabric made of a cellulose-based blended filament yarn and a method for manufacturing the same and, more specifically, to a method for providing a fabric made of a cellulose-based blended filament yarn with highly enhanced dyeing properties by performing a dyeing process using a blended filament yarn produced from a specific cellulose resin and a specific polyester resin.

Description

[0001] The present invention relates to a cellulose-based mixed yarn and a dyeing method thereof,

The present invention relates to a method for dyeing a cellulose hornblend fabric fabric and a cellulose hornblende fabric fabric excellent in dyeability.

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 plasticizer volatilization inside the chip and other large amount of gas are generated during the melt spinning with the chip using the conventional thermoplastic cell rollerose derivative, the workability is not good and the physical properties of the yarn are remarkable due to the thermal stability and lack of viscosity of the melted resin. .

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, conventional biodegradable cellulose ester-based fibers have a problem in that it is difficult to develop for various applications because of low physical properties.

On the other hand, stretchability is a characteristic that synthetic fibers can not be easily expressed, and is regarded as an intrinsic property of natural fibers such as wool. Conventional techniques for imparting stretchability to synthetic fibers include (1) a method of producing two kinds of synthetic fibers (yarns) having a large difference in elongation property by compression-twisting-thermo-setting to produce this shrinkable composite false- A method of mixing polyurethane fibers and other synthetic fibers having excellent stretchability in the longitudinal direction at the time of manufacturing, and (3) methods of producing conjugated fibers by complex spinning of two types of polymers.

Among the above methods, the method of producing the shrinkage composite false-twist yarn is a method of giving potential difference in shrinkage ratio by twisting two kinds of yarns having large differences in elongation properties in a pseudo-twisted state. In other words, by using the difference of deformation ratio and residual deformation ratio after cracking in the flammable region to the maximum extent, it is more distorted in judging and superimposition, and is intertwined with judging. The shrinkage composite false-twist yarns exhibit good stretchability due to differences in elongation properties between the yarn and the warp yarn during heat treatment in the post-treatment process. However, this method is disadvantageous in that the expression state of the crimp is non-uniform and the binding force between the crimp and the superpowder depends on air entanglement or the like, so that one component yarn is separated or removed by the physical force applied during the post- there was.

In addition, the biodegradable cellulose ester-based fibers have a drape property and an absorbency when they are used alone to produce a cloth for a garment outerwear. However, there is a problem that the fabric is easily damaged due to low strength, In the case of fabric fabrics made of cellulose ester fibers, there is a problem in that the dyeability is poor.

Therefore, it is an urgent point to develop a hornblende which is capable of maintaining or improving the biodegradability of the conventional biodegradable cellulose ester-based fibers, as well as having high strength and high stretchability and improved dyeability, and a fabric using the same.

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

Disclosure of the Invention The present invention has been conceived in order to solve the problems as described above, and it is an object of the present invention to provide a cellulose fiber which is produced by mixing a thermoplastic cellulose ester fiber prepared by using a cellulose ester resin derived from a specific pulp, And a method of dyeing the same.

In order to solve the above problems, the present invention relates to a cellulose fiber having excellent dyeability, wherein the cellulose fiber is a cotton fiber, and the fiber is a thermoplastic cellulose fiber; And a composite fiber in which polytrimethylene terephthalate (PTT) and polyethylene terephthalate (PET) fibers are side-by-side-combined spinning fibers.

In one preferred embodiment of the present invention, the fiber-reinforced synthetic resin fibers constituting the fabric of the present invention include thermoplastic cellulose ester fibers (hereinafter referred to as CE fibers) and conjugated fibers in a weight ratio of 100: 20 to 45 do.

In one preferred embodiment of the present invention, the CE fiber comprises a cellulose resin, a plasticizer, a radical formation inhibitor and a radical activity inhibitor, wherein 25 to 45 parts by weight of a plasticizer, 0.01 to 50 parts by weight of a radical generation inhibitor To 2 parts by weight, 0.01 to 2.5 parts by weight of the radical activity inhibitor, and 1 to 5 parts by weight of a color pigment.

As a preferred embodiment of the present invention, the cellulose resin of the C.E fiber component may be characterized in that it is derived from a pulp satisfying the following Equation 1 and Equation 2 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 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 a preferred embodiment of the present invention, the cellulose resin of the CE fiber component 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 , A glass transition temperature of 185 ° C to 195 ° C, and a moisture content of 2% by weight to 4% by weight.

As a preferred embodiment of the present invention, in the present invention, the cellulose resin of the CE fiber component has a viscosity of 100 to 130 poise when measured according to ASTM D1343, and is dispersed in the CAB solution according to the Pt-Co standard The color is 220 to 350 ppm in the measurement and the haze is 35 to 50 ppm in the measurement according to ASTM D871.

As a preferred embodiment of the present invention, in the present invention, among the CE fiber components, the cellulose resin has a compaction bulk density of 410 kg / m ³ to 450 kg / m ³ and a pored bulk density ) Is 300 kg / m ³ to 340 kg / m ³ .

In one preferred embodiment of the present invention, the cellulose resin of the CE fiber component 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.

In one preferred embodiment of the present invention, the plasticizer of the CE fiber component 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, Ethyl citrate, and the like.

In one preferred embodiment of the present invention, the radical generation inhibitor of the CE fiber component comprises a water insoluble compound including a phenol group, and the radical activity inhibitor comprises a water insoluble compound containing phosphorus at the terminal .

In one preferred embodiment of the present invention, the radical generation inhibitor of the CE fiber component is 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 the like.

In one preferred embodiment of the present invention, the radical activity inhibitor of the CE fiber component is at least one selected from tris (2,4-di-t-butylphenyl) phosphite and tris-nonylphenyl phosphite and triphenyl phosphite And a control unit.

In one preferred embodiment of the present invention, the CE fiber is prepared by processing a cellulose ester resin containing the cellulose resin, a plasticizer, a radical formation inhibitor and a radical activity inhibitor, and the cellulose ester resin is prepared according to ASTM D1238 And has a melt viscosity of 95.0 Pa.sec to 160.0 Pa.sec, a heat flow of 60 g / 10 to 120 g / 10 min, and a shear rate of 120 / s to 160 / s as measured at 260 ° C .

In another preferred embodiment of the present invention, the PTT of the conjugate fiber has an intrinsic viscosity (IV) of 0.90 dl / g to 1.10 dl / g, and the PET has an intrinsic viscosity (IV) of 0.50 dl / 0.65 dl / g.

In another preferred embodiment of the present invention, the composite fibers according to the present invention may have an average fineness of 20 to 100 denier.

In another preferred embodiment of the present invention, the composite fiber may include PTT and PET in a weight ratio of 45:55 to 50:50.

According to a preferred embodiment of the present invention, in the present invention, the fibrin glue yarn has a total fineness of 50 to 200 de and an entanglement number of 5 to 20 fragments / m.

As one preferred embodiment of the present invention, the present invention is characterized in that the fiber-reinforced synthetic fiber has an elastic recovery of 35% to 50%, a strength of 1.0 g / de to 3.0 g / de and a fracture elongation of 20% to 45% .

As one preferred embodiment of the present invention, in the present invention, the isosurfactant yarn may be an ITY (Interlace Yarn), an ATY (Air-Jet Textured Yarn), a DTY (Draw Textured Yarn), a composite yarn yarn or a covering yarn .

Another object of the present invention is to provide a method of dyeing a cellulose-based mixed filament yarn fabric with excellent dyeability, comprising the steps of: pre-treating a cellulose-based mixed filament yarn fabric into a pretreatment solvent; Dyeing the pretreated fabric into a salt solution; And removing unreacted dyes in the saline solution containing the dyed fabric, thereby dyeing the fabric of the cellulosic fibers.

In a preferred embodiment of the present invention, the pretreatment solvent in the pretreatment step comprises NaOH in a concentration of 0.5 g / L to 2.0 g / L and a scouring agent in a concentration of 1.5 g / L to 3 g / L, . &Lt; / RTI >

In one preferred embodiment of the present invention, the scouring agent may include at least one selected from a nonionic surfactant and an anionic surfactant.

In a preferred embodiment of the present invention, the scouring agent is selected from the group consisting of ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and triethylene glycol monobutyl Ether, or a nonionic surfactant containing at least one selected from the group consisting of anionic surfactants and ethers.

In a preferred embodiment of the present invention, the temperature of the pretreatment solvent before the introduction of the fabric is 15 ° C to 35 ° C, the temperature of the fabric is increased to 2.5 ° C / min to 4 ° C / And then the fabric is pre-treated at 100 ° C to 120 ° C for 30 minutes to 90 minutes.

As a preferred embodiment of the present invention, the pretreatment step may be performed at a pH of 9 to 11.

In one preferred embodiment of the present invention, the dye solution of the dyeing step is characterized by containing 1.0% o.w.f. to 2.5% o.w.f of disperse dye and 0.1% o.w.f. to 0.7% o.w.f of dispersing agent.

In one preferred embodiment of the present invention, the disperse dye in the salt liquid component is selected from azo based disperse dyes, anthraquinone based disperse dyes, Dinitrophenyl amin based disperse dyes and quinoline based disperse dyes And may include one or more species.

In one preferred embodiment of the present invention, the dispersant may include at least one selected from anionic dispersants and nonionic dispersants.

In a preferred embodiment of the present invention, the dispersing agent is Prestabit oil V, Anionic dispersants comprising at least one selected from AH (Avirol. AH), Igepon T, Eulysine A and Eunaphthol AS; And a nonionic dispersant comprising at least one selected from the group consisting of Peregal O, Noigen, and Lenenole; , And the like.

In one preferred embodiment of the present invention, the dyeing step is performed at pH 4 to 4.5 and at 105 to 120 ° C for 30 to 60 minutes.

In one preferred embodiment of the present invention, the step of removing the unreacted dye comprises a step of applying a reducing bleaching agent having a concentration of 2 g / L to 5 g / L and a reducing bleaching agent having a concentration of 1 g / L to the 1 L of the distilled water containing the dye- And then adding NaOH at a concentration of ~3.5 g / L to remove the unreacted dye.

As a preferred embodiment of the present invention, the step of removing the unreacted dye may be performed at 60 ° C to 80 ° C for 10 minutes to 40 minutes.

The fabric of the present invention is produced by introducing thermoplastic cellulose ester fiber and polyethylene terephthalate fiber produced by using a cellulose resin derived from a specific pulp at an optimum ratio and using the fiber of the present invention to have a high strength and high stretchability, And can provide an environmentally friendly functional fabric material excellent in biodegradability.

FIG. 1 is a schematic view of a dyeing process of the present invention for facilitating understanding of the present invention. FIG.
Fig. 2 is a photograph of the dyed hornblende fabric prepared in Comparative Production Example 1. Fig.
Fig. 3 is a photograph of the dyed horn sheath fabric prepared in Production Example 1. Fig.
Fig. 4 is a schematic view of a composite spinning device used in the manufacture of an isosceles horn of the present invention.

Hereinafter, the present invention will be described in detail.

In order to ensure excellent high strength and high stretchability, the present invention introduces specific conjugate fibers and introduces thermoplastic cellulose ester fibers prepared using a cellulose ester resin synthesized from specific pulp-specific pulp in order to improve the biodegradability and dyeability The present invention also relates to a fabrics fabric produced by using the same,

The fiber-reinforced composite yarn may be an ITY (Interlace Yarn), an ATY (Air-Jet Textured Yarn), a DTY (Draw Textured Yarn), a composite yarn or a covering yarn.

First, a description will be given in detail of the yarn sheath yarn used in manufacturing the fabric of the present invention.

The fibrin fiber used in the present invention includes thermoplastic cellulose ester fiber (hereinafter referred to as CE fiber); And a conjugated fiber prepared by side-by-side-type conjugated spinning of polytrimethylene terephthalate (PTT) and polyethylene terephthalate (PET) fibers, wherein the CE fiber and the conjugate fiber are mixed at a weight ratio of 100:20 to 45, By weight, and more preferably 100: 30 to 40 by weight. If the amount of the PET fiber is less than 20 parts by weight, the stretchability may deteriorate. If the amount of the PET fiber is less than 20 parts by weight, the stretchability may exceed 45 parts by weight and the stretchability may be excellent.

First, the CE fiber used in the present invention will be described. The CE fiber according to the present invention includes a cellulose resin, a plasticizer, a radical formation inhibitor, and a radical activity inhibitor, and is produced by melt-spinning using a mixed resin thereof .

In the present invention, the cellulose resin is produced by synthesizing a pulp 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 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 may be lowered when the cellulose resin is melted and the melt processability may be deteriorated. When the degree of substitution of the cellulose ester resin is 2.8 There is a problem that not only the biodegradability is lowered but also the cellulose resin is carbonized at the time of melt spinning 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.

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. 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 be reduced. Therefore, the weight average molecular weight It is good to use.

The cellulose 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. The cellulose resin is excellent in heat resistance and can be melt-spun at a high temperature.

The moisture content of the cellulose 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 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. The cellulose ester resin used in the conventional melt spinning method had a viscosity of 10 poise to 60 poise, but the cellulose ester resin synthesized from the specific pulp of the present invention had 100 poise to 130 poise, which can greatly improve the high temperature melt radiation at high temperature have.

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

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 plasticizer, which is one of the CE fiber components of the present invention, is not particularly limited as far as it is mixed with a cellulose resin so as to prevent strong hydrogen bonding due to hydroxyl groups present in the cellulose resin and to allow melt spinning. More preferably, The weight average molecular weight is preferably 350 to 750, and more preferably 400 to 650. [ 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 CE fiber of the present invention includes a radical generation inhibitor and a radical activity inhibitor. When the cellulose resin is thermoplasticized or the plasticized cellulose resin is chipped and melted before it is radiated, And it plays a role of preventing decomposition and suppresses generation of radicals generated by breaking the chain, so that it is possible to spin at a 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.

The C.E fiber of the present invention can be used not only as a radical generation inhibitor but also as a radical activity inhibitor, thereby providing 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 2.5 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 cellulose ester resin melted in the thermoplastic or melt spinning process may be thermally decomposed. If the amount exceeds 2.5 parts by weight, there may be a problem in workability and moldability as a cause of an increase in pack pressure.

The mixed resin has a melt viscosity of 95.0 Pa.sec to 160.0 Pa.sec when measured according to the ASTM D1238 method and a melt flow index at 260 DEG C, Lt; RTI ID = 0.0 > Pa.sec < / RTI > to 140 Pa.sec.

The mixed resin had a heat flow rate of 60 g / 10 min to 120 g / 10 min, a shear rate of 120 / s to 160 / s, and a melt viscosity May be between 95 Pa.sec and 160 Pa.sec.

Hereinafter, the present invention will be described in detail with reference to a method for producing C.E fiber constituting the fibers of the present invention.

The method for producing C.E fiber comprises the steps of: preparing a mixed resin by mixing a cellulose resin, a plasticizer, a radical formation inhibitor and a radical activity inhibitor; Adding the mixed 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 chip through a spinneret to produce a thermoplastic cellulose ester fiber.

A cellulose resin, a plasticizer, a radical formation inhibitor, a radical activity inhibitor and a coloring dye in the step of producing the mixed resin, and the characteristics, usage, etc. of these compositions are the same as those described above.

Next, the step of preparing the melted cellulose ester chips will be described. In the blending of the step of producing the melted cellulose ester chips, the internal temperature of the kneader is preferably 160 ° C to 240 ° C To 210 DEG C, and more preferably from 165 DEG C to 205 DEG C. If the internal temperature of the kneader is less than 150 DEG C, the resin is not melted sufficiently and the resin is not kneaded smoothly There may be a problem of releasing 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, It is better to perform blending.

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.

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 265 to 290 ° C, preferably at a spinning speed of 2,200 to 2,900 mpm and a spinning temperature of 270 to 285 ° C, A speed of 2,300 to 2,800 mpm and a spinning temperature of 270 ° C to 280 ° 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 265 DEG C, 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. If the spinning temperature exceeds 290 DEG C, 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 uniformity of the yarn is poor due to the low back pressure applied to the detention. 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.

Next, the composite fibers constituting the shrinkable filament yarn used in the fabric of the present invention will be described.

The composite fiber may include a melt forming step of melting polytrimethylene terephthalate (PTT) and polyethylene terephthalate (PET), respectively, and a step of spinning the melt at a spinning speed of 4,500 to 6,000 m / min to form a side- (FDY), which comprises the steps of:

And the stretching temperature in the step of obtaining the drawn fiber (FDY) is 60 ° C to 95 ° C. Further, the present invention may further include a step of heat treating the drawn fiber (FDY) at 110 ° C to 130 ° C after the step of obtaining the drawn fiber (FDY).

The intrinsic viscosity (IV) of the PTT may be from 0.90 dl / g to 1.10 dl / g, the intrinsic viscosity (IV) of PET may be from 0.50 dl / g to 0.65 dl / g, Is less than the above range, the fluidity is increased, the winding property is lowered, and the adhesion between the interfaces is significantly lowered. If the intrinsic viscosity exceeds the above range, there is a problem in workability in spinning. In the case of PET, When the difference in viscosity is small, the elasticity is deteriorated. When the stretching properties of the conjugated fibers are tested by various combinations of the viscosities of the PTT and PET polymers, it is advantageous to increase the viscosity difference between the two polymers to exhibit stretching properties.

The content ratio of PTT to PET can be used in a weight ratio of 45:55 to 50:50. At this time, if the ratio of PTT exceeds 50, there is a drawback that the stretchability is deteriorated.

The composite fiber thus produced has a fracture elongation of 30% to 45%, a maximum stress value of dry heat shrinkage stress of 0.2 G / D to 0.5 G / D, a temperature of 180 ° C to 220 ° C at the time of dry heat shrinkage maximum stress, The shrinkage length after LEESONA measurement is 30 cm to 40 cm, the elasticity recovery rate is 35% to 50%, and the number of alternating lines is 5 to 20 pieces / m.

It is preferable that the composite fibers have an average fineness of 20 to 100 denier, preferably an average fineness of 25 to 70 denier, more preferably 30 to 50 denier, to secure the strength and stretchability of the cross- .

The composite spinning can be performed using a composite spinning apparatus shown in a schematic view of FIG. 4, and more specifically, through a melting step through an extruder 1 into which PTT and PET are injected, The individual fibrous polymer emitted through the first godet roller 3 is passed through a spinning pack 2 and a spinning pack 2 including a side-by-side spinneret under the spinneret, (Full Drawn Yarn; FDY) is produced and heat-treated in the second godet roller 5 to obtain a side-by-side composite fiber.

The composite fiber is produced by completely drawing a drawn fiber (FDY) by stretching in one step at the same time as spinning. Unlike the conventional method in which a conventional melt is produced by partially stretching (POY) and then drawn through a stretching step, unlike the method of producing the PTT and the PET melt by just one stage of stretching, The drawn drawn fiber (FDY) is produced, and a separate second elongating step is not necessary, which leads to a process shortening effect.

The composite spinning is preferably performed at 4,500 m / min to 6,000 m / min, and preferably at a spinning speed of 4,500 m / min to 5,500 m / min. The spinning process is faster than the conventional composite spinning speed of 2,000 m / min to 3,500 m / min. The fibers have a new texture with a good feeling of compactness and softness and stretch due to the single-step drawing and the high speed. In addition, productivity can be improved. Therefore, if the fiber spinning speed exceeds 6,000 m / min, the spinning workability is remarkably decreased, which may cause problems in producing the fibers. If the spinning speed is less than 4,500 m / min, There is a fear that the elasticity can not be achieved, and a partial unevenness of the crimp occurs, thereby making it difficult to produce a uniform fiber.

In addition, in the stretching step, it is very important to set proper conditions as a factor that greatly affects the crimp characteristics of the conjugate fiber at the stretching temperature and the stretching ratio. The stretching temperature of the present invention is preferably 60 占 폚 to 95 占 폚. When the stretching temperature is less than 60 캜, the uniformity of the fibers is deteriorated and the quality is poor. When the stretching temperature exceeds 95 캜, the workability is deteriorated and the fibers may be easily broken.

Further, the heat treatment temperature is also an important factor, and the heat treatment temperature can be appropriately adjusted to adjust the temperature of the pole-responsive power to improve the crimp property, preferably 110 to 130 ° C. If the heat treatment is carried out below the above range, the shear fluctuation of the composite fibers is severely generated. If the heat treatment exceeds the above range, the workability is poor and the manufacturing cost is increased.

The method for producing the fiber of the present invention used in the fabric of the present invention as described above will be described in more detail with reference to a process of mixing the CE fiber and the conjugate fiber and then passing the mixed fiber through a stretcher , Winding the mixed fibers in the stretching machine 5 to 6 times from the first godet roller, passing through the heating plate, and winding the sheet 4 to 6 times with the second godet roller.

Also, the temperature of the first godet roller is 100 ° C. to 130 ° C., the temperature of the heating plate is 170 ° C. to 195 ° C., and the sheet is passed through a stretching machine at a winding speed of 600 mpm to 1200 mpm, Can be produced.

The production method and characteristics of the C.E fiber and the composite fiber are the same as those described above.

The total number of strands is 50 to 200 d, and the total number of strands is 75 to 150 d, preferably 7 strands / m To 15 pieces / m.

The above-mentioned isosurfactant yarn may have an elastic recovery rate of 35% to 50%, a strength of 1.0 g / de to 3.0 g / de and a breaking extension of 20% to 45% %, A strength of 1.2 g / de to 2.5 g / de and a elongation at break of 25% to 35%.

Then, the cellulose fiber can be manufactured by weaving the produced fiber of the present invention.

Next, a description will be given of a method of dyeing the fabric of cellulose-based mixed filament yarn. The fabric can be produced by the same method as the outline process shown in FIG. 1. Specifically, Introducing a raw material into a pretreatment solvent and pretreating the raw material; Dyeing the pretreated fabric into a salt solution; And removing unreacted dyes of the saline solution containing the dye-treated fabric fabric.

The pretreatment solvent in the pretreatment step comprises NaOH at a concentration of 0.5 g / L to 2.0 g / L and a scouring agent at a concentration of 1.5 g / L to 3 g / L, relative to 1 L of distilled water, wherein the concentration of NaOH is 0.5 g / L, there may be a problem that the pH of the pretreatment solvent is too low, and the pH is excessively higher than 2.0 g / L, so that the surface is saponified by NaOH and the dyeability by the disperse dye is lowered. If the concentration of the scouring agent is less than 1.5 g / L, there may be a problem that the dyed fabric is not uniformly removed due to uneven removal of the foaming agent and foreign matter generated during the fabric manufacturing, and the concentration of the scouring agent is 3 g / L, the dyability can not be further improved and there may be an uneconomical problem.

The temperature of the pretreatment solvent before the introduction of the fabric in the pretreatment step is 15 ° C to 35 ° C, preferably 20 ° C to 30 ° C. After the fabric is charged into the pretreatment solvent, After raising the temperature to 100 ° C to 120 ° C at a heating rate of 4 ° C / minute, the fabric can be pretreated at 100 ° C to 120 ° C for 30 minutes to 90 minutes, preferably 50 minutes to 80 minutes. At this time, it is effective to carry out pretreatment at a pretreatment temperature of 80 ° C to 120 ° C, preferably at 100 ° C to 120 ° C. At this time, even if the pretreatment is carried out at a temperature higher than 120 ° C, it is not economical since the dyeing effect is not improved. Therefore, it is preferable to perform the pretreatment within the temperature range.

The pH of the pretreatment solvent in the pretreatment step is preferably 9 to 11. When the pH is less than 9, it is difficult to uniformly remove the adhesive agent and the foreign matter generated during the manufacture of the fabric, And when the pH exceeds 11, the pH becomes too high, so that the surface is saponified by NaOH, and the dyeability by the disperse dye may be deteriorated.

Next, the saline solution in the dyeing step includes a disperse dye and a dispersant, wherein the disperse dye is selected from azo-based disperse dyes, anthraquinone-based disperse dyes, Dinitrophenyl amin-based disperse dyes, quinoline Quinoline) disperse dyes.

The dispersant may be at least one selected from the group consisting of an anionic dispersant and a nonionic dispersant. Preferably, the dispersant is Prestabit oil V, Anionic dispersants comprising at least one selected from AH (Avirol. AH), Igepon T, Eulysine A and Eunaphthol AS; And a nonionic dispersant comprising at least one selected from the group consisting of Peregal O, Noigen, and Lenenole; May be used.

If the concentration of the disperse dye is 1.0% owf ~ 2.5% owf, it may be less than 1.0% owf, and if the concentration of the disperse dye is less than 1.0% owf, It is uneconomical since there is no further improvement in dyeability. If the concentration of the dispersing agent is less than 0.1% owf, the dyeing may not be uniformly performed on the fabric, and if the concentration of the dispersing agent is less than 0.1% owf, the concentration of the dispersing agent may be 0.7% owf It is not economical since there is no further improvement in dyeability even when it is used in excess. Therefore, it is preferable to use it within the above range.

The dyeing step may be carried out at a pH of 4 to 4.5 and at a temperature of 105 to 120 ° C, preferably at a pH of 4 to 4.5 and at a temperature of 110 to 120 ° C for 30 to 60 minutes. If the pH of the salt solution is less than 4 Or when the pH exceeds 4.5, there may be a problem that the dyeability by the disperse dye is lowered. If the temperature is lower than 105 ° C in the dyeing process, there may be a problem that the dyeability of polyethylene terephthalate stained at a high temperature is lowered. If the temperature is higher than 120 ° C, the cellulose acetate has a problem that the dyeability at high temperature is lowered There may be a problem that not only the dyeability of the hornblende fabric fabric composed of species is lowered but also the two-tone phenomenon occurs.

Next, the unreacted dye may be removed by immersing it in a distilled water containing a dyed fabric, followed by stirring at 60 ° C to 80 ° C for 10 minutes to 40 minutes.

The distilled water may contain a reducing bleaching agent having a concentration of 2 g / L to 5 g / L and NaOH having a concentration of 1 g / L to 3.5 g / L with respect to 1 L of distilled water.

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 1-1: Preparation of Thermoplastic Cellulose Ester Fiber

(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 0.1 part by weight of tris (2,4-di-t-butylphenyl) phosphate (Alcanox 240, Chemtura 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 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) Production of Thermoplastic Cellulose Ester (C.E) Fibers

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 CE fibers having a fineness of 100 denier.

Example 1-2

CE fibers were prepared in the same manner as in Example 1 except that the cellulose acetate resin prepared in Preparation Example 2 was used instead of the cellulose acetate resin prepared in Preparation Example 1 .

Comparative Example One

The procedure of Example 1-1 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 to obtain a thermoplastic cellulose ester fiber .

Comparative Example 2

The same thermoplastic cellulose ester fiber as in Example 1 was prepared in the same manner as in Example 1-1 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 .

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

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 5 and Comparative Examples 1 and 2, were measured at 260 ° C according to ASTM D1238, The results are shown in Table 2 below.

division Melting point
(Pa.sec) Heat flowability
(g / 10 min) Shear rate
(S ^-1 ) Example 1-1 133.1 81.6 147.2 Examples 1-2 125.6 86.9 151.4 Comparative Example 1-1 27.3 220.4 312.8 Comparative Example 1-2 57.6 135.2 184.3

Example 2-1

PTT having an intrinsic viscosity of 1.10 dl / g and PET having an intrinsic viscosity of 0.55 dl / g were simultaneously spinning at a spinning speed of 5,000 m / min using the composite spinning apparatus shown in the schematic diagram of Fig. 4 to measure the temperature of the first godet roller (Stretching temperature) of 70 占 폚 and a heat treatment temperature of 120 占 폚 to prepare a side-by-side composite fiber having a mono-denier of 1.25 denier and an average fineness of 30 denier.

Example 2-2

Side-by-side type composite fibers were prepared in the same manner as in Example 2-1, except that the mono-denier had a fineness of 2.1 denier and an average fineness of 50 denier.

Example 3-1: This Island Fulham Produce

C. E fibers having an average fineness of 100 denier prepared in Preparation Example 1-1 and the conjugate fibers of Example 2-1 having an average fineness of 30 denier were prepared.

Next, the two different fibers were wound five times on a first godet roller set at 110 DEG C using a suction gun at one time, and then guided to a heating plate set at 180 DEG C and wound four times on a second godet roller And then the island of Hyeongseongsa was produced. At this time, the winding speed of the stretching machine is 700 mpm, and the prepared fiber has a fineness of 150 denier and the number of interlaced fibers is 13 fibers / m.

Example 3-2 ~ Example 3-4 and Comparative Example 3-1 ~ Comparative Example 3-4

Except that the CE fibers prepared in Example 1-2 were used in place of the CE fibers prepared in Example 1-1, and the same interlocking yarns were prepared in the same manner as in Production Example 1, 3-2.

Examples 3-3 to 3-4 and Comparative Examples 3-1 to 3-4 were carried out as shown in Table 3 to prepare an isosbestic filament yarn.

division C.E fiber
Kinds Conjugated fiber
C.E fiber and PET Fiber weight ratio Total fineness
(Denier) Interchange Example 3-1 Example 1-1 Example 2-1 100: 30 130 13 pieces / m Example 3-2 Example 1-1 Example 2-2 100: 50 150 13 pieces / m Example 3-3 Examples 1-2 Example 2-1 100: 30 130 13 pieces / m Example 3-4 Examples 1-2 Example 2-2 100: 50 150 13 pieces / m Comparative Example
3-1 Comparative Example 1 Example 2-1 100: 30 130 13 pieces / m Comparative Example
3-2 Comparative Example 1 Example 2-2 100: 50 150 13 pieces / m Comparative Example
3-3 Comparative Example 2 Example 2-1 100: 30 130 13 pieces / m Comparative Example
3-4 Comparative Example 2 Example 2-2 100: 50 150 13 pieces / m

Experimental Example 2 : This Island Horn Temple Property measurement

Strength, elongation at break and shrinkage of the false-twisted yarns prepared in Production Examples 1 to 6 and Comparative Production Examples 1 to 4 were measured according to the following methods, and the results are shown in Table 4 below.

(1) Measurement of strength and elongation at break

The fineness was calculated by weighing 90 m of the tare which is 1 m when it was rotated once, and converting it into 9,000 m. The strength and the elongation at break of the fiber were measured by an automatic tensile tester.

(2) Elastic recovery rate Measure

Measured according to ASTM D6720. The sample is adjusted in rotation speed by fineness so that 5,000 denier can be obtained, and immersed in water at 100 ° C for 15 minutes to measure L1 and L2 as follows.

L1: After applying 30g + 1000g load, measure (stress & relax 3 times)

L2: 1000g Load removal 30 seconds later, measurement

[Equation 1]

Elastic recovery rate (%) = {(L1 - L2) / L2} x 100 (%)

division Horn Temple
Strength (g / de) Horn Temple
Elongation at break (%) Elasticity Recovery Rate (%) Example 3-1 1.7 28 41 Example 3-2 2.2 31 43 Example 3-3 1.4 26 37 Example 3-4 1.9 27 39 Comparative Example 3 -One Non-manufacturing Comparative Example 3 -2 Non-manufacturing Comparative Example 3 -3 0.8 18 27 Comparative Example 3 -4 0.9 19 31

As shown in Table 4, in the case of Comparative Example 3-1 in which CE fibers constituting the hornblende yarn were used and the CE fibers prepared by using the cellulose acetate resin of Comparative Example 1 were used, the radiation workability was very poor Hence, it was impossible to manufacture Horn Island. In addition, in Comparative Example 3-2 using CE fiber prepared using cellulose acetate resin which has been commercially available and sold in the past, although some spinning was possible, the strength and elongation were so low that the rate of increase in physical properties There is a problem that the appearance is not very good and the elastic recovery rate is also very low.

On the other hand, when the fineness of the conjugate fiber was changed to 30 denier and 50 denier, the mechanical properties of the conjugate fiber increased as the fineness of the conjugate fiber increased. This was because the relative strength of the conjugate fiber .

In the case of Examples 3-1 to 3-4, it was confirmed that the strength was 1.2 g / de or more, the elongation at break 25% or more, and the shrinkage rate was 37% or more.

Manufacturing example One : This Island Horn temple history Cellulose system used Horn Temple Fabric Fabrication

(1) The cellulosic horseshoe filament fabrics were prepared with the warp densities of 140 filaments / inch and weft density of 120 filaments / inch, prepared in Example 3-1.

(2) Next, a pretreatment solvent having a pH of 9.8 to 10.0 was prepared by adding 1 g / L of NaOH and 2 g / L of a scouring agent (mixed at a weight ratio of ethylene glycol monomethyl ether and ethylene glycol monobutyl ether 1: 0.5) to distilled water .

After the fabric of the horn sheathed yarn was put into the pretreatment solvent (25 ° C), the temperature raising rate was raised to 3 ° C per minute to 100 ° C, and then the horn sheathed fabric was pretreated at 100 ° C for 60 minutes. At this time, 2.0 parts by weight of the fabric of hornbush fabric was added to 100 parts by weight of the pretreatment solution to perform pretreatment.

(3) Next, 2.5% owf of disperse dye for acetate fiber (Lumacell Blue HA) and dispersant (Sunsalt RM-340) were prepared by preparing a dyeing solution containing 0.3% owf and adjusted to pH 4.3 with acetic acid aqueous solution, The fabric was added in an amount of 1.0 part by weight and the dyeing process was performed at 110 캜 for 40 minutes.

(4) Next, 3 g / L of a reducing bleaching agent (Na ₂ SO ₄ ) and ₂ g / L of NaOH were added to 1 L of distilled water and mixed. Then, the dyed fabric was added thereto and treated at 70 ° C. for 20 minutes The reaction (fastening) dye was removed and the final dyed horn sheathed textile fabric was prepared.

Fig. 3 shows a photograph of the fabric of the horns yarn fabric which was dyed.

Manufacturing example 2

A dyed horny sheath fabric fabric was prepared in the same manner as in Preparation Example 1 except that a disperse dye for acetate fiber (Lumacell Blue HA) and a disperse dye for polyester fiber (Dystar Co., Dianix Blue) were mixed at a weight ratio of 1: 3 Then, a dyeing solution containing 2.5% owf of the mixed disperse dye and 0.3% owf of the dispersing agent (Sunsalt RM-340) was prepared, and the dyeing process was carried out in the same manner as in Preparation Example 1 To prepare a dyed Hornsusa textile fabric.

Manufacturing example 3

A dyed horny sheath fabric fabric was prepared in the same manner as in Preparation Example 1 except that a disperse dye for acetate fiber (Lumacell Blue HA) and a disperse dye for polyester fiber (Dystar Co., Dianix Blue) were mixed at a weight ratio of 1: 1 Then, a dyeing solution containing 2.5% owf of the mixed disperse dye and 0.3% owf of the dispersing agent (Sunsalt RM-340) was prepared, and the dyeing process was carried out in the same manner as in Preparation Example 1 To prepare a dyed Hornsusa textile fabric.

Manufacturing example 4

A dyed hornblende fabric fabric was prepared in the same manner as in Preparation Example 2 except that a disperse dye for acetate fiber (Lumacell Blue HA) and a disperse dye for polyester fiber (Dystar Co., Dianix Blue) were mixed at a weight ratio of 1: 1 Thereafter, a dyeing solution containing 2.0% owf of the mixed disperse dye and 0.3% owf of the dispersing agent (Sunsalt RM-340) was prepared, and the dyeing process was performed in the same manner as in Preparation Example 1 To prepare a dyed Hornsusa textile fabric.

Comparative Manufacturing Example One

Except that the disperse dyes for polyester fibers (Dystix, Dianix Blue) were used alone instead of the disperse dyes for acetate fibers to prepare dispersed dyes of 2.5% owf and The dispersing agent (Sunsalt RM-340) was prepared by dyeing a dyeing solution containing 0.3% owf and then dyeing the same by the same method as in Production Example 1 to prepare a dye-treated hornbush yarn fabric. 2

Comparative Manufacturing Example 2

The dyed horn sheathed textile fabric was prepared in the same manner as in Comparative Preparation Example 1 except that the fabric was dyed at 120 ° C for 40 minutes instead of 110 ° C.

Comparative Manufacturing Example 3

The disperse dye 3.0% owf and the dispersant (Sunsalt RM-340) were dispersed in a 0.3% aqueous solution using a disperse dye (Dystar, Dianix Blue) alone, owf was prepared, and a dyeing process was carried out in the same manner as in Comparative Preparation Example 1 using the dyeing solution.

Comparative Manufacturing Example 4

(1) Cellulose acetate fibers prepared from 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 were conventionally used for producing a molten cellulose ester yarn, / inch, and a weft density of 120 yarns / inch, to prepare a cellulose acetate fabric cloth.

(2) Next, the cellulose acetate fabric fabric was subjected to pretreatment and dyeing processes in the same manner as in Preparation Example 1 to prepare cellulose acetate fabric fabrics stained with the cellulose acetate fabric.

Comparative Manufacturing Example 5 ~ Comparative Manufacturing Example 6

Comparative Production Example 5 was performed by carrying out the dyeing process at 85 캜 for 40 minutes and the dyeing process was carried out at 130 캜 for 40 minutes to obtain Comparative Production Example 6 To prepare a horn sheath yarn fabric subjected to dyeing treatment.

Experimental Example 3: Evaluation of dyeability of dyed fabric

The dyeability of the fabric fabrics prepared in Production Examples 1 to 4 and Comparative Production Examples 1 to 6 was measured by a spectroscopic colorimeter (CM-3600D, manufactured by KONICA MINOLTA). The results are shown in Table 6 below.

In Table 5, the degree of dyeing is represented by a K / S value, which is a numerical value indicative of the concentration of dyeing on the fabric fabric surface.

In Table 5, the degrees of improvement in the two-tone development were evaluated by visual comparison and relative comparison with the surface adhesion concentration 9.3, which was measured when dyeing fabric fabrics made only with cellulose acetate fibers (⊚: B: large improvement, B: improvement, X: not improved).

As can be seen from the above Table 5, in the case of Production Examples 1 to 4, the K / S value as the surface dyeing concentration was significantly improved as compared with Comparative Production Examples 1 to 3 using the disperse dye for polyester fiber, It was confirmed that the two-tone phenomenon was also improved by the comparison of FIG. 2 (Comparative Production Example 1) and FIG. 3 (Production Example 1).

In Comparative Production Example 4 and Comparative Production Example 6 where the dyeing temperature was less than 105 占 폚 and exceeded 120 占 폚 in the dyeing step, As compared with Production Example 2, the result showed that the concentration of the dye was greatly reduced.

It can be confirmed that the two-tone phenomenon improvement and the K / S value can be obtained when the hornbath yarn of the present invention and the dyeing process under the specific conditions are performed through Production Examples 1 to 4, and the content of the disperse dye for acetate fibers is The higher the value, the better the K / S value.

1: extruder 2: spinning pack
3: first godet roller 4: fused yarn (FDY)
5: second godet roller

Claims

This island also includes the Horn Island temple,
Thermoplastic cellulose ester fibers; And
A composite fiber in which polytrimethylene terephthalate (PTT) and polyethylene terephthalate (PET) fibers are side-by-side-type conjugated fibers;
Wherein the cellulose fiber has an excellent dyability.

The method according to claim 1, wherein the thermoplastic cellulose ester fiber and the conjugate fiber are contained in a weight ratio of 100:20 to 45,
Wherein the thermoplastic cellulose ester fiber comprises a cellulose resin, a plasticizer, a radical formation inhibitor, and a radical activity inhibitor, and the cellulosic fibers have excellent dyeability.

The cellulose resin according to claim 2, wherein the cellulose resin is derived from a pulp satisfying the following Equation (1) and Equation (2): Cellulosic hornblende fabric having excellent dyeability;
[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 method according to claim 2, wherein the cellulose 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% Which is excellent in dyability.

The thermoplastic cellulose ester fiber according to claim 2, wherein the thermoplastic cellulose ester fiber 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 2.5 parts by weight of the radical activity inhibitor, And 5 parts by weight of a cellulose-based woven fabric.

The PET according to claim 1, wherein the PTT has an intrinsic viscosity (IV) of 0.90 to 1.10 dl / g, and the PET has an intrinsic viscosity (IV) of 0.50 dl / g to 0.65 dl / g. Synthetic woven fabric of Osus system.

The fabric according to claim 1, wherein the conjugate fiber comprises the PTT and the PET in a weight ratio of 45:55 to 50:50.

[3] The fabric according to claim 1, wherein the filament yarn has a total fineness of 50 to 250de and an interlocking number of 5 / m to 20 / m.

9. The dye-sensitized solar cell according to any one of claims 1 to 8, characterized in that the resilience of the seamed yarn is 35% to 50%, the strength is 1.0 g / de to 3.0 g / de and the elongation at break is 20% to 45% Excellent cellulosic woven fabrics.

9. The dye-sensitized solar cell according to any one of claims 1 to 8, wherein the blended yarn is at least one of ITY (Interlace Yarn), ATY (Air-Jet Textured Yarn), DTY (Draw Textured Yarn) Improved cellulose based woven fabrics.

Subjecting the fabric of horns yarn fabric of claim 9 to pretreatment solvent;
Dyeing the pretreated fabric into a salt solution; And
Removing the unreacted dye of the saline solution including the dyed fabric fabric;
&Lt; RTI ID = 0.0 > 1. &Lt; / RTI > A method of dyeing a cellulose-based hornblende fabric fabric.

12. The method according to claim 11, wherein the pretreatment solvent in the pretreatment step comprises NaOH in a concentration of 0.5 to 2.0 g / L and a scouring agent in a concentration of 1.5 to 3 g / L,
Wherein the scouring agent comprises at least one selected from a nonionic surfactant and an anionic surfactant.

13. The method of claim 12 wherein the scouring agent is selected from the group consisting of ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and triethylene glycol monobutyl ether. Wherein the nonionic surfactant is at least one nonionic surfactant.

The method according to claim 11, wherein the temperature of the pretreatment solvent before the introduction of the fabric raw material in the pretreatment step is 15 ° C to 35 ° C,
After the fabric is put into a pretreatment solvent, the temperature is raised from 100 ° C to 120 ° C at a temperature raising rate of 2.5 ° C / min to 4 ° C / min, and then the fabric is pretreated at 100 ° C to 120 ° C for 30 minutes to 90 minutes &Lt; / RTI > wherein the cellulose-based hornblende yarn is dyed.

12. The method according to claim 11, wherein the pretreatment step is performed at a pH of 9 to 11. 11. A method for dyeing a cellulose-

12. The method of claim 11, wherein the saline solution comprises 1.0 to 2.5% owf of disperse dye and 0.1 to 0.7% owf of dispersant.

17. The method of claim 16, wherein the disperse dye comprises at least one selected from azo-based disperse dyes, anthraquinone-based disperse dyes, Dinitrophenyl amin-based disperse dyes, and quinoline-
Wherein the dispersing agent comprises at least one selected from an anionic dispersant and a nonionic dispersing agent.

The method according to claim 11, wherein the dyeing step is performed at a pH of 4 to 4.5 and a temperature of 105 to 120 ° C for 30 to 60 minutes.

12. The method of claim 11, wherein removing the unreacted dye comprises: applying a reducing bleach at a concentration of 2 to 5 g / L and NaOH at a concentration of 1 to 3.5 g / L to 1 liter of distilled water containing the dye- To remove the unreacted dye. The dyeing method of the cellulose-based mixed filament yarn fabric according to claim 1, wherein the unreacted dye is removed.

The method according to claim 11, wherein the step of removing the unreacted dye is performed at 60 ° C to 80 ° C for 10 minutes to 40 minutes.