TW201002907A - Method for producing dyed fabric structure - Google Patents

Abstract

Disclosed is a method for producing a dyed fabric structure which has not only biodegradability but also excellent wear resistance and soft texture. Also disclosed are a fabric structure and an automobile interior material. Specifically, a fabric structure which contains polylactic acid fibers having a melting point as measured by DSC of not less than 195 DEG C is dyed, and then, if necessary, formed into an automobile interior material.

Description

201002907 IX. OBJECT OF THE INVENTION [Technical Field] The present invention relates to a method for producing a dyed fiber structure, and more particularly to the manufacture of a dyed fiber structure of a fiber structure containing polylactic acid fibers method. [Prior Art] The polylactic acid fiber is excellent in so-called biodegradability, and is therefore used in various aspects such as automobile interior materials, household articles, clothing materials, and the like (see Patent Document 1, Patent Document 2, and Patent Document 3). However, since the melting point of the polylactic acid fiber is lower than that of the aromatic polyester such as polyethylene terephthalate, when the fiber structure containing the polylactic acid fiber is dyed, the polylactic acid fiber is caused by the thermal history of the hot color. The wire strength is lowered, resulting in a problem of reduced wear resistance. Therefore, polylactic acid fibers are hardly used in the field where abrasion resistance is required. Further, the present applicant proposed a filter containing a high-melting polylactic acid fiber in Japanese Patent Application No. 2007-1 44736. (Patent Document 1) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2003-105. A dyed fiber structure having a soft texture and excellent abrasion resistance and washing fastness is provided. -5-201002907 The inventors of the present invention have conducted a review on the production method of the polylactic acid, and found that when the polylactic acid fiber having a high melting point is used as the polylactic acid fiber in the dyeing of the fiber structure containing the polylactic acid fiber, a soft texture can be obtained. The present invention has been completed by a dyed fiber structure excellent in abrasion resistance and washing fastness. Therefore, according to the present invention, there is provided a method for producing a dyed fibrous structure, characterized in that a fibrous structure comprising a polylactic acid fiber having a melting point of 195 ° C or higher is dyed. In this case, the polylactic acid fiber preferably contains (i) poly L-lactic acid (component A) having a weight average molecular weight of 50,000 to 300,000, and (ii) poly D-lactic acid (component B) having a weight average molecular weight of 50,000 to 300,000. And (iii) a total of 100 parts by weight of each of the a component and the B component, containing 0.5 to 5 parts by weight of the phosphate metal salt represented by the following formula (i) or (2):

In the formula (1), R! represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 and r3 each independently represent a hydrogen atom or a hospital group having a carbon number of 1 to 12, and Μι represents a metal atom or an alkaline earth metal atom. , p means 1 or 2, -6 - 201002907

(2) In the formula (2), R4, R5 and r6 each independently represent a hydrogen atom or an alkyl group having a carbon number of 1 to η, M2 represents an alkali metal atom or an alkaline earth metal atom, and p represents ruthenium or ruthenium, polylactic acid. The fiber preferably contains 0.1 to 5 parts by weight of the carbonium imine compound per 100 parts by weight of the total of the L-lactic acid component and the poly-D-lactic acid component, and is treated in boiling water at 130 ° C for 30 minutes. The molecular weight retention rate is 85 % or more. The monofilament fineness of the polylactic acid fiber is preferably in the range of 0.01 to 20 dtex. Further, the filament strength of the polylactic acid fiber is preferably 2.5 cN/dtex or more. Other fibers may also be included in the fibrous structure. Other fibers are preferably polyethylene terephthalate fibers. The fibrous structure is preferably woven or knitted. The dyeing temperature is preferably in the range of 110 to 140 °C. After the dyeing treatment, the reduction washing treatment is preferably carried out. The reduction washing treatment is preferably carried out in a reduction bath having a pH of from 8 to 2 at a temperature of from 6 Torr to 98 °C. After dyeing, it is preferred to impart an enamel resin, a polyethylene resin or a polyethylene terephthalate resin to the fiber structure. The present invention encompasses a dyed fiber structure produced by the above production method. The fiber strength of the polylactic acid fiber contained in the fiber structure is preferably from -7 to 201002907 2 · 3 cN/dtex or more. The fiber strength of the polylactic acid fiber contained in the fiber structure after one week of treatment in an environment of a temperature of 7 C ° C and a humidity of 90% RH is preferably 〇·5 cN/dtex or more. The fibrous structure is preferably a fabric having a basis weight of from 30 to 1,000 g/m2. The fiber structure is preferably a fabric having a planar wear resistance of 3 or more. The brightness index (L値) of the fiber structure is preferably 80 or less. Fiber structure The washing fastness measured by the AATCC IIA method is preferably at least grade 3. The present invention comprises a fiber product selected from the group consisting of a clothing material, a clothing material, an automobile interior material, a household product, an industrial material, and a small article composed of the above-mentioned fiber structure. [Embodiment] Hereinafter, the present invention will be described in detail. <Polylactic acid> The polylactic acid used in the present invention is preferably a fiber composed of polylactic acid containing a poly-L-lactic acid component and a poly-D-lactic acid component. In particular, a fiber composed of a crystalline poly-L-lactic acid component or a poly-D-lactic acid component is preferred. It is preferably a fiber composed of a poly-L-lactic acid component having a high optical purity and a polylactic acid component of a poly-D-lactic acid component. Further, a crystalline poly L-lactic acid component having a melting point of 160 t: or more or a poly D-lactic acid component can be suitably used. The poly L-lactic acid component used in the present invention preferably contains 90 to 100 mol%, more preferably 95 to 100 mol% of the L-lactic acid unit, and is preferably 99 to 100 m in order to achieve a high melting point. The % of the ear is preferably composed of a 95% to 99 mol% 2 L-lactic acid unit with a degree of stereochemistry. As for other D-lactic acid units, units of copolymerization other than lactic acid. The unit of the copolymerization component other than lactic acid is 0 to 1 mol%, Μ%, more preferably 〇1 mol%. The poly-D-lactic acid component is preferably 90-100 mol%, more preferably the ear D-lactic acid unit, and in order to achieve a high melting point, the ear% is additionally obtained, and if the stereoscopic degree is taken as a priority, the The D-lactic acid unit is preferably constituted. As for other units, an example of a copolymerization component other than L-lactic acid is used. The unit of the L-lactic acid unit and the copolymerization component is 〇 10 10 mol%, preferably 0 to 5 mol 0 to 1 mol %. The unit of the copolymerization component is exemplified by a dicarboxylic acid having a functional group capable of forming a double bond, a polyvalent alcohol, a hydroxycarboxylic acid, various polyesters, various polycarbonates, and the like which are formed by the various constituent components. Unit. Examples of the dicarboxylic acid are succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid and the like. The polyvalent alcohol is exemplified by a diol, a propane diol, a butane diol, a pentane diol, a hexane diol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, polyethylene glycol, An aromatic substance such as an alcohol such as polypropylene glycol or polytetramethylene glycol or an addition of ethylene oxide to bisphenol. As the hydroxycarboxylic acid, for example, glycolic acid, hydroxybutyric acid, 4-, etc. As for the lactone, for example, glycolide, ε-hexine vinegar, and g, the amount of the unit is D-lactic acid, and the unit is 〇~5, which is 95~1, 〇〇莫为99~1 〇〇莫〃 9 9 mole % of lactic acid unit, % other than lactic acid, more preferably more than one ester ester unit, various polyether azelaic acid, ethylene glycol, propylene glycol, octane alcohol, triethylene di-aliphatic Valence of polyvalent alcohols such as hydroxybenzoic acid, ε-hexene-9- 201002907 ester, yS-propiolactone, (5-butyrolactone, /3- or 7-butyrolactone, valerolactone, 5 - Valerolactone, etc. The poly-L-lactic acid component and the poly-D-lactic acid component preferably have a weight average molecular weight of from 1,000,000 to 50,000, more preferably from 15,000 to 350,000. In addition, as long as the weight of the polymer is When the amount of other components is 1% by weight or less, it is also possible to blend other components. Poly L-lactic acid and poly-D-lactic acid can be produced by a known method. For example, L- or D-lactide can be present in a metal polymerization catalyst. It is produced by heating under a ring-opening polymerization. Further, after the low molecular weight polylactic acid containing a metal polymerization catalyst is crystallized, the solid phase is heated under a reduced pressure or an inert gas stream. Further, it can be produced by polymerization, and can be produced by direct polymerization of lactic acid by dehydration polymerization in the presence/absence of an organic solvent. The polymerization can be carried out in a conventional reaction vessel, for example, a spiral belt can be used alone or in parallel. A vertical reactor or a horizontal reactor with a high-viscosity stirring wing, etc. Alternatively, it may be either batch or continuous or semi-batch, or a combination thereof. Alcohol may also be used as the polymerization. The initiator is preferably one which does not inhibit the polymerization of the polylactic acid. For example, decyl alcohol, dodecanol, tetradecanol, cetyl alcohol, stearyl alcohol, etc. may be suitably used. The solid phase polymerization method uses a lower molecular weight lactic acid polyester obtained by the above ring-opening polymerization method or direct lactic acid polymerization method as a prepolymer. The prepolymer is a melting point (Tm) which is less than the glass transition temperature (Tg) thereof. It will be pre-crystallized in the temperature range, but it can be better in terms of preventing melting. The crystallized prepolymer is charged to a fixed vertical or horizontal reactor, or a drum-10-201002907 or Kiln-shaped container The rotatable reaction vessel (rotary kiln and heated to a temperature range of the glass transition temperature (Tg) of the prepolymer or more, (Tm). The polymerization temperature does not cause any problem even if the temperature is raised with the polymerization. In order to effectively remove the water generated in the combination, a method of decompressing the above reaction vessel or circulating a heated inert gas stream may be preferably employed. The metal catalyst used in the polymerization of the polylactic acid is preferably a final deactivator. Insulating. The deactivating agents are exemplified by, for example, a group of organic ligands derived from a chelating ligand obtained on a polymeric metal catalyst. Dihydroquinoxaline (I) acid, dihydrogen Tetracalyx II, II) acid, hydrogen trioxoquine (III) acid, dihydropentaquinic acid, hydrogen pentaquine diphosphonate (Π, ιν) acid, tauquinine hexaphosphate, hydrogen octacidine Triphosphorus (ΙΠ, ΐν, ΐν) acid, octosaquivalent triphosphoric acid, hydrogen hexahydroquine diphosphorus (III, V) acid, hexahydroquine diphosphorus (decapine tetraphosphoric acid) The low oxidation number of acid number valence of 5 or less such as quinoxaphosphoric acid tetrakis(VI) acid (V, IV, IV) acid is exemplified by the formula χΗ20· yP2〇5 The orthophosphoric acid represented by x/y = 3 is 2 > x / y > 1, a polyphosphoric acid called diphosphoric acid, triphosphoric acid, pentaphosphoric acid or the like and a mixture thereof. Further examples include metaphosphoric acid, especially trimoephosphoric acid and tetrametaphosphoric acid. Further, a part of the phosphorus pentoxide structure represented by l>x/y>0 has a cage-type superphosphoric acid (collectively referred to as a metaphosphoric acid compound). Also wait for the acidic acid salt. Further, a partial ester or a complete ester of the acid and the monovalent or polyvalent polyalkylene glycol can be exemplified. Further, in the furnaces and the like, the quinodiphosphine (phosphorus (III) (III) acid IV, III, IV IV composed of an imine group is not known as the internal melting point of the solid phase clustering. ) Acid, > ENEA Phosphoric Acid. Another. Further, an example of tetraphosphoric acid, which is specifically represented by x/y = i, is a molecular structure of the alcohol or an acid of the phosphorus -11 - 201002907 generation of a lower aliphatic carboxylic acid derivative. It is better to be deactivated by the catalyst, preferably by the formula xH20. yP2〇5, x/y = 3 orthophosphoric acid. Further, it is preferably 2>X/y>l, which is called polyphosphoric acid such as acid, triphosphate, tetraphosphoric acid or pentaphosphoric acid, and the like by the degree of condensation. Further, it is preferably a metaphosphoric acid represented by x/y = 1, especially a trimetaphosphorus. Preferably, the phosphorus pentoxide structure represented by l>x/y> 具有 has a cage-mesh structure of superphosphoric acid (these are collectively referred to as metaphosphoric acid compounds). Further preferred are acidic salts of such acids. Further preferred are partial esters of such acids with polyvalent alcohols or polyalkylene glycols. Further, it is preferably such a phosphorus oxaquine acid or such an acidic ester. Further, it is preferably a lower aliphatic carboxylic acid derivative or the like. It is also preferred to use the above metaphosphate. The metaphosphoric acid-based compound used in the present invention comprises a cyclic metaphosphoric acid obtained by condensing an acid unit of about 3 to 200 or a domain metaphosphoric acid having a three-dimensional network structure or the like (alkali metal salt, alkaline earth metal salt, key salt: In particular, it is preferred to use a cyclic aliphatic sodium hydride or a super-aliphatic carboxylic acid derivative substituted with a sodium metaphosphate in the super field to be referred to as DHPA). The lactide content of the polylactic acid used in the present invention is selected in the range of 〇 ppm. It is preferably in the range of 0 to 500 ppm, more preferably in the range of 0 to 10 ppm, and in the range of 0 to 10 ppm. By making the polylactic acid have the lactide content in the range, the stability at the time of melting can be improved, and the advantage of being effective and stable spinning can be obtained and the hydrolysis resistance of the fiber product can be improved. The content of the lactide is lowered in this range, and can be obtained by the phosphorous super-collar of the acid-phosphorus, such as poly-L-lactic acid and poly-D-diphosphide mixed acid, a monovalent monovalent acid, etc. In the optimum stage of the polymerization of the lactolactic acid -12-201002907 to the end of the production of the polylactic acid, it is achieved by performing the conventional lactide mitigation treatment or combining the above. The polylactic acid used in the present invention. The weight average molecular weight is preferably from 100,000 to 500,000, more preferably from 100,000 to 300,000, and even more preferably from 105,000 to 250,000. The weight average molecular weight (Mw) and the number average molecular weight (Μη) of the polylactic acid. The ratio is referred to as molecular weight dispersion (Mw/Mn). The large molecular weight dispersion means that the ratio of large molecules to small molecules is larger than the average molecular weight, that is, polylactic acid having a large molecular weight dispersion, for example, a weight average molecular weight is Under the condition of about 250,000, the polylactic acid having a molecular weight dispersion of more than 3 has a large molecular weight ratio of 2 more than 250,000, and in this case, since the melt viscosity becomes large, the spinning and elongation steps are involved. Poor. The polylactic acid having a small weight average molecular weight and a large molecular weight dispersion of about 100,000 has a weight average molecular weight of less than 1 million. In this case, the mechanical properties of the fiber are durable. It is smaller and less preferable to use. From this point of view, the molecular weight dispersion range is preferably from 1.5 to 3.0, more preferably from 1.5 to 2.5, still more preferably from 1.6 to 2.5. The number average molecular weight is measured by gel permeation chromatography (GPC) using chloroform as a solution to determine the weight average molecular weight and number average molecular weight of the standard polystyrene. Poly L-lactic acid component and poly in polylactic acid The weight ratio of the D-lactic acid component is in the range of 90:10 to 10:90, preferably in the range of 7 5:2 5 to 25:7 5 , more preferably in the range of 60:40 to 40:60, and as much as possible It is preferably close to 50:50. Polylactic acid preferably contains a sterically miscible polylactic acid composed of a poly-L-lactic acid component and a poly-D-lactic acid component. The content of the sterically misaligned polylactic acid, that is, the stereo-13-201002907 degree It is dissolved in the temperature rising process in the differential scanning calorimeter (DSC) measurement In the crucible, the ratio of the dissolution peak 对应 corresponding to the steric miscible crystal is preferably from 80 to 100%, more preferably from 95 to 100°, in the following formula (a). The melting point in the present invention is determined by DSC. The crystal melting peak temperature is used in the presence of a low temperature crystal melting peak temperature and a steric misaligned crystal melting peak temperature. The melting point of the polylactic acid is 195 ° C or more ' preferably 195 to 2 50 ° C, more preferably 200 to 240 ° C is extremely important. The steric miscible crystal melting enthalpy is preferably 20 J/g or more, more preferably 30 J/g or more. Stereotacticity = [(AHms/AHmsO)/(AHmh/AHmsO + AHms/ AHmsO)]x 1 00 (a) (where AHms0 = 203.4J/g, AHmhO=142J/g, AHms = steric complex melting point Melting 焓, ΔΗηι1ι = melting of crystallization). The polylactic acid can be produced by mixing the poly L-lactic acid component alone or by coexisting and mixing the poly L-lactic acid component and the poly D-lactic acid component in a specific weight ratio. Mixing can be carried out in the presence of a solvent. The solvent is not particularly limited as long as it can dissolve poly-L-lactic acid and poly-D-lactic acid, but is preferably, for example, chloroform, dichloromethane, dichloroethane, tetrachloroethane, phenol 'tetrahydrofuran, N-methyl group. A single or a mixture of two or more of succinyl ketone, N,N-dimethylformamide, butyrolactone, trioxane, and hexafluoroisopropanol. Further mixing can be carried out in the absence of a solvent. Alternatively, a method of mixing and mixing poly-L-lactic acid and poly-D-lactic acid in a specific amount may be employed, and any one of them may be melted and added to the other and kneaded. -14- 201002907 Alternatively, a poly-L-lactic acid fragment and a poly-D-lactic acid fragment may be combined, and a stereoblock polylactic acid may be suitably used as the polylactic acid. The stereoblock polylactic acid is a block polymer in which a poly-L-lactic acid fragment and a poly-D-lactic acid fragment are combined in a molecule. Such a block polymer may be previously used, for example, by a method of successive ring-opening polymerization; a method of polymerizing poly-L-lactic acid and poly-D-lactic acid followed by a chain exchange reaction or a chain extender; and making poly-L-lactic acid A method of polymerizing and blending poly-D-lactic acid, a chain extension method by solid phase polymerization, a method of producing a block copolymer having the above basic constitution by a method of stereoselective ring-opening polymerization catalyst production from racemic lactide . However, a high-melting-point solid block polymer obtained by sequential ring-opening polymerization is preferred because it is easy to manufacture when a polymer obtained by a solid phase polymerization method is used. The polylactic acid and the stereoblock polylactic acid used in the present invention preferably have a stereochemistry of 90% or more, more preferably 100%. The degree of stereochemistry can be determined by the above formula (a) by comparing the melting point of the D S C measurement. The polylactic acid used in the present invention is preferably formed by adding a specific additive to stabilize and highly forming a stereo compound phase. For example, a metal phosphate salt represented by the following formulas (1) and (2) is exemplified as a preferred example: -15- 201002907

In the formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (the alkyl group having 1 to 4 carbon atoms is exemplified as methyl group, ethyl group, n-propyl group, n-butyl group, second group). Butyl, isobutyl and the like. R_2, R3, each of which is a single atomic group or a carbon number of 1 to 12, and the alkyl group of 1 to 12 is exemplified by methyl, ethyl, n-propyl, isopropyl', second butyl, isobutyl. , tert-butyl, pentyl, third pentylene, heptyl, octyl, isooctyl, trioctyl, 2-ethylhexyl, isodecyl, fluorenyl, isodecyl, third fluorenyl , undecyl, mono-, tert-dodecyl and the like. M represents an alkali metal atom such as Na, K or Li or a halogen atom such as Mg or Ca. P represents 1 or 2. The phosphate metal salt represented by the formula (1) preferably has a hydrogen atom and R2 and R3 are all a third group. Take 1 isopropyl group. Carbon number n-butyl group, hexyl fluorenyl group, one yard base soil type gold for example -16- 201002907

(2) In the formula (2), R4, R5 and R6 each independently represent an alkyl group having 1 to 12 hydrogen atoms. The alkyl group having 1 to 12 carbon atoms is exemplified by methyl, ethyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, tert-pentyl, hexyl, heptyl, octyl Base, isooctyl, third temple ethylhexyl, decyl, isodecyl, fluorenyl, isodecyl, tert-alkyl, dodecyl, tert-dodecyl and the like. M2 represents an alkali metal atom such as Na, K or Li or an alkali atom such as Mg or Ca. P represents 1 or 2. Preferred among the phosphate metal salts represented by the formula (2) are those in which R4 and R6 are a methyl group and R5 is a third butyl group. Phosphate metal salt ADEKA (shares) trade names NA-11 and NA-71. Phosphate esters can be synthesized by conventional methods. The compound represented by the formula (2) is known as a polylactic acid-depleted crystal nucleating agent, as described in JP-A-2003-128884. However, in the present invention, it is characterized by % in the formula (1), the formula (2), and a metal atom or an alkaline earth metal atom. In the case of formula (1), formula Μ! and M2 is other metals such as aluminum, the compound itself is low, sublimation occurs during spinning, and it is difficult to spin, carbon number n-propyl, pentyl: The base, the 2-base, the ten earth-based gold is, for example, a metal salt) or (the compound M2 is the heat-resistant -17-201002907 phosphate metal salt (component C) in the test (2), and the average primary particle diameter is preferably 0.01. ~10#m, more preferably 〇·〇5~7//m. The particle size is less than O.Oiym has difficulty in the industry, and it is not necessary to be so small. If it is larger than 10 μm, it is spun and extended. The frequency of the broken metal wire becomes high. The content of the phosphate metal salt is 1 part by weight, preferably 0.05 to 5 parts by weight, more preferably 0.05 to 0.5, per 1 part by weight of the poly-L-lactic acid component and the poly-D-lactic acid component. The part by weight is more preferably 0.05 to 0.2 part by weight. When the amount is too small, the effect of increasing the degree of stereochemistry is small, and when it is too much, the resin itself may be deteriorated and not good. The polylactic acid used in the present invention may suitably have a specific functional group. The carboxyl blocking agent acts as a moisture and heat resistance improving agent, wherein the carboxyl group is effectively blocked and the polylactic acid fiber is promoted From the viewpoints of the hue of the dimensional structure, the formation of the stereocomplex phase, the heat and humidity resistance, etc., it is preferred to select a carbodiimide compound having a specific functional group of a carbodiimide group. Examples of sub-zero female compounds are dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbamate Yttrium, octyl decyl carbodiimide, di-t-butyl carbodiimide, tert-butyl isopropyl carbodiimide, bis- carbodiimide, diphenyl Carbodicarbonimine, N-octyldecyl-N,-phenylcarbodiimide, N-nodal-fluorene-p-phenylene diimenimine, N-pyringyl Ν -'-toluene Carbon bis quinone imine, di-o-tolyl fluorenyl carbodiimide, bis-k-carbyl hydrazinyl fe-fee 'bis(p-nitrophenyl) carbodiimide, Bis(p-aminophenyl)carbodiimide, bis(p-hydroxyphenyl)carbodiimide, bis(p-chlorophenyl)carbodiimide, bis(o-chlorophenyl) ) carbodiimide, bis(o-ethylphenyl)carbodiimide, double (pair _ -18- 2010029) 07 ethyl phenyl) carbodiimide, bis(o-isopropylphenyl)carbodiimide, bis(p-isopropylphenyl)carbodiimide, bis(o-iso-butyl) Phenyl)carbodiimide, bis(p-isobutylphenyl)carbodiimide, bis(2,5-dichlorophenyl)carbodiimide, p-phenylene O-tolylhydrylcarbodiimide), p-phenylene bis(cyclohexylcarbodiimide), p-phenylene bis(p-chlorophenylcarbodiimide), 2,6 , 2',6'-tetraisopropyldiphenylcarbodiimide, hexamethylenebis(cyclohexylcarbodiimide), ethylidene bis(phenylcarbodiimide), stretch Ethyl bis(cyclohexylcarbodiimide), bis(2,6-dimethylphenyl)carbodiimide, bis(2,6-diethylphenyl)carbodiimide, double (2-ethyl-6-isopropylphenyl)carbodiimide, bis(2-butyl-6-isopropylphenyl)carbodiimide, bis(2,6-diisopropyl) Phenyl)carbodiimide, bis(2,6-di-t-butylphenyl)carbodiimide, bis(2,4,6-trimethylphenyl)carbodiimide , bis(2,4,6-triisopropyl Carbodiimide, bis(2,4,6-tributylphenyl)carbodiimide, di-/3-naphthylcarbodiimide, N-tolyl-oxime'·cyclohexyl A mono- or dicarbodiimide compound such as carbodiimide or fluorenyl-tolyl-fluorene-p-phenylcarbodiimide. Among them, in terms of reactivity and stability, bis(2,6-diisopropylphenyl)carbodiimide, 2,6,2',6'-tetraisopropyl-based carbon Monoacid imide is preferred. Further, industrially available dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferably used. In addition, examples are poly(1,6-cyclohexanecarbodiimide), poly(4,4,-methylenebiscyclohexylcarbodiimide), poly(1,3_cyclohexylenecarbyl)醯imine), poly(I,4-cyclohexylenecarbodiimide), poly(4,4'--19- 201002907 diphenylmethane carbodiimide), poly(3,3'- Dimethyl-4,4'-dimethane carbodiimide), poly(naphthalene carbodiimide) 'poly(p- carbodiimide), poly(m-phenylene carbene) Imine), polytolylcarbodiimide, poly(diisopropylcarbodiimide), methyldiisopropylphenylene carbodiimide, poly(triethylbenzenediamine) Imino), such as polycarbodiimide. As for the commercially available polycarbodiimide compound, for example, "CARBOZILITE" sold by Minqing (share) can be used, and specifically, "CARBOZILITE" LA-1, which is sold as a polylactic acid resin modifier, can be exemplified as the polyester resin. "CARBOZILITE" HMV, etc. for the sale of modifiers. The carbodiimide compound can be produced by a conventional method. It can be produced by using an organic phosphorus compound or an organometallic compound as the catalyst 7 (at a temperature above TC, without solvent or by decarbonation condensation reaction of the organic isomer in an inert solvent. Further, the polycarbodiimide compound is used in the past The production method of the known polycarbodiimide compound is manufactured, and the specification of U.S. Patent No. 2,941,956 is known as 'Tokyo Sho 47-33279. 1 0 r g. Chem. 28, 2069-2075 (1963) ' Chemical Review Vol. 8 1 No. 4, p6 1 9-62 1 , etc. The content of the carbodiimide compound is preferably 0.1 to 5 parts by weight, more preferably 0.5 parts by weight per 100 parts by weight of the total of the poly-L-lactic acid component and the poly-D component. 〜2 parts by weight. The ligated polylactic acid fiber containing the carbodiimide compound in the range is treated with boiling water at 1 ° C for 30 minutes to obtain a fiber having a retention rate of 95% or more. It is also possible to use phenyl phenyl benzene (p-poly (based on carbon spinning as -8C A, for example, in cyanic acid, for example, J. 1981, - lactic acid is good as a choice of 00-201002907) A conventional carboxy terminal blocking agent. The carboxyl group in the present invention The reactive terminal blocking agent not only blocks the carboxyl group at the end of the polylactic acid, but also blocks the carboxyl group generated by the decomposition reaction of polylactic acid or various additives or the carboxyl group of a low molecular compound such as lactic acid or citric acid. It is preferred to block not only the carboxyl group but also the hydroxyl terminal of the acidic low molecular compound by thermal decomposition or to block the moisture invading the resin composition. The carboxyl terminal blocking agent is preferably selected from the ring. At least one compound of an oxygen compound, an oxazoline compound, an oxazolidine compound, and an isocyanate compound is preferably an epoxy compound, an oxazoline compound, or an isocyanate compound. As the epoxy compound, a glycidyl ether compound can be suitably used, and the compound can be used. a glyceride compound, a glycidylamine compound, a glycidyl ruthenium compound, a glycidyl decylamine compound, or an alicyclic epoxy compound. By containing a terminal carboxyl blocking agent, not only the action of the carbamide compound can be enhanced, Further, fibers excellent in spinnability, mechanical properties, heat resistance, and durability can be obtained. In the lactic acid, the terminal blocking agent and various additives described later may be blended in any stage of polymerization in the ring-opening polymerization method, and preferably added to the direct reaction vessel at the later stage of polymerization. Considering uniform dispersion and hue in the polylactic acid. In the case of deterioration prevention, it is preferable to knead with an extruder or a kneader, that is, the polymer discharge port of the reactor may be connected to a single-shaft or multi-axis extruder, and it may be exemplified to add various kinds of agents. After the polymerization, the granulated polylactic acid or the polylactic acid powder after the solid phase polymerization, and the method of mixing - 21 - 201002907 by an extruder or a kneader. At this time, various additives may be directly metered into the extruder or the kneader in a molten liquid, an aqueous solution or an organic solvent solution or dispersion, or may be slowly added to the polylactic acid by a side feeder. It is also preferred to carry out the mixing with the polylactic acid in the main batch of granules or fine powder by an extruder or a kneader. <Polylactic acid fiber> The polylactic acid fiber can be obtained by spinning and stretching the above polylactic acid according to a conventional method. In this case, the extension may be a plurality of extensions of one or more stages, and the stretching ratio is preferably 3 times or more, more preferably 4 times or more, and more preferably 4 to 10 times from the viewpoint of producing high-strength fibers. . The extension preheating may be a flat or needle contact heating in addition to the temperature rise of the rolls. The stretching temperature is preferably from 7 Torr to 140 ° C, more preferably from 80 to 130 ° C. Further, the heat treatment after stretching is preferably from 170 to 200 ° C, more preferably from 180 to 200 ° C under tension. The heat treatment can be carried out by a heating roll, a contact heater, a non-contact heating plate or the like. The fiber composed of the polylactic acid thus obtained is measured by a differential scanning calorimeter (DSC), and it is extremely important that the melting peak temperature (melting point) is 195 5 or more. When the melting point is lower than 1 95 °C, the strength of the fiber is lowered due to thermal history during dyeing, which is not preferable because it shrinks and hardens. Further, the higher the melting point, the better, but 240 ° C or less is sufficient. Further, the filament strength of the polylactic acid fiber is preferably 2.5 cN/dt ex or more, preferably about 3.0 cN/dtex. The higher the upper limit, the better, but it is actually around 10 cN/dtex. Further, from the viewpoint of the texture of the fiber structure, the monofilament fineness of the polylactic acid-22-201002907 acid fiber is preferably from 0.01 to 20 dtex', more preferably from 0.1 to 7 dtex. The total fineness is 30 to 500 dtex, and the number of fibers is preferably in the range of 20 to 200. <Fiber structure> The fiber structure can be obtained by weaving the above polylactic acid fiber. At this time, the fiber may be subjected to twisting or air processing, false twist crimping, or the like. In particular, the application of the twisted yarn of about 100 to 600 T/m to the fiber not only improves the abrasion resistance of the fiber structure, but also improves the workability in the production of the woven fiber structure. Further, it is preferred to use only a woven fiber structure made of polylactic acid fiber, but it may contain other fibers. The content of the other fibers is preferably 5.0% by weight or less based on the weight of the fiber structure. As other fibers, polyethylene terephthalate fibers and the like are exemplified. Further, the structure of the fiber structure is not particularly limited, but is preferably a woven or knitted fabric woven by a general loom or knitting mechanism. In any case, it is preferably a fibrous structure composed of a non-woven fabric or a matrix fiber and a heat-bonding fiber. For example, the weaving structure of the fabric is exemplified by the three original tissues of plain weave, twill weave, and forged weave, and the plain weave, double weave, double weave, etc. The type of knitting can be a circular weft (weft weaving) or a warp. The structure of the circular weave (weft weaving) is preferably woven as a warp knitting, rib knitting, double weaving, double reverse weaving, hanging stitch weaving, floating weaving, semi-twisting weaving, yarn weaving, weaving, etc. It is exemplified by a single comb, a flat weave, a single comb, a satin knit, a double combed orange, a -23-201002907 flat weave, a pile warp, a jacquard weave, and the like. The number of layers can be more than one layer. Further, it may be a bristles and a bottom tissue fiber structure composed of cut velvet (1 ο 〇 ppi 1 e). <Staining> Before dyeing, it may be at a temperature of 50 to 100 °. C is subjected to a reduction treatment under alkali conditions at a weak basicity of 80 to 100 ° C. Further, after dyeing, a dry heat treatment is preferably carried out at a temperature of 140 to 180 ° C. The fiber structure can be dyed by the following methods. Although a good azo-based disperse dye is preferably exemplified as the dye, it is not particularly limited to a disperse dye diester-based disperse dye or an azo-based disperse dye which is decomposed by a solution in a cleaning treatment liquid to be described later. The thiophene type. Further, the dyeing temperature of the fluorenone-dispersed ketone-type disperse dye and the disperse dye having an alkylamine group is preferably 110 to 140 ° C, more preferably 120. The dyeing time is good. When the fiber structure contains polyethylene terephthalate polyester fiber as the other fiber, it is preferably used in an aqueous dye solution containing a leveling agent, a pH adjuster, or the like. Better 120~135 °C or more At the temperature, the fiber structure which is subjected to 20~ 〇 dyeing treatment is preferably subjected to reduction, the single layer may be 2 piles, and/or the bristles are formed by scouring or before the temperature dyeing and/or the color is dispersed. For washing fastness this. In particular, it is exemplified by a dyeing treatment which is preferably a disperse dye having a temperature of a thiazole type material, a benzofuranone to a temperature of 1 to 3 ° C, and a temperature of preferably 120 ° C for 40 minutes. . In the case of -24-201002907, the reduction washing treatment is preferably carried out in a reduction bath of pH 8 to 2. In an alkaline region larger than p Η 8, polylactic acid fibers are decomposed to lower the fiber strength. Examples of the reducing agent include a tin-based reducing agent, a white powder C, a white powder, a vaporized tin, a sulfinic acid-based reducing agent, and a hydrogen sulfate. The concentration of the reducing agent is preferably from 1 to 10 g/liter, and the concentration is preferably selected depending on the type of dye used, the dyeing concentration, and the temperature of the reduction bath. The treatment temperature of the reduction bath is not particularly limited, but is preferably in the range of 60 to 98 ° C, and the treatment time is preferably from 10 to 40 minutes. Therefore, the 'reduction washing treatment is preferably carried out in a reduction bath of pH 8 to 2 at a temperature of 60 to 98 °C. Further, as the fiber swelling agent, a commonly used dyeing agent such as a chlorobenzene-based dyeing agent, a methylnaphthalene-based dyeing agent, or an o-phenylphenol-based system may be used as the fiber swelling agent. A dye-inducing agent, an aromatic ether-based dyeing agent, an aromatic ester-based dyeing agent, and the like. The fiber swells may, for example, be polyoxyethylene alkyl aryl ethers, polyoxyethylene alkylamines, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl ethers, polyoxyethylenes which are considered to have affinity for fibers. The alkylamine ether, the polyoxyethylene alkylalkylbenzylammonium chloride, the alkyl chloride methyl chloride key, etc. are not limited thereto. When the reduction washing treatment is carried out in a weakly alkaline to acidic region at a pH of 8 or less, the polylactic acid fiber is not hydrolyzed at the time of the reduction washing treatment, and the dye of the surface portion of the remaining fiber can be reduced and decomposed. Further, it is preferable to impart an enamel resin, a polyethylene resin or a polyethylene terephthalate resin to the fiber structure after the "dyeing". The resin can be imparted to the fiber structure by pad dyeing or the like. It is preferable to impart a resin to the fiber structure to improve the abrasion resistance of the high fiber structure of -25 to 201002907. At this time, the amount of the resin adhered is preferably in the range of 0.5 to 5.0% by weight based on the weight of the fiber structure. Furthermore, before and/or after the dyeing step, water absorption processing, water repellent processing, raising processing, flame retardant, ultraviolet shielding or antistatic agent, antibacterial agent, deodorant, insect repellent, light storage agent, Retroreflectors, negative ion generators, and the like impart various functions to the processing. <Fiber Structure Characteristics> The present invention includes the fiber structure obtained by the above method. In the obtained fiber structure, the fiber density of the polylactic acid fiber contained in the fiber structure is preferably 2.3 cN/dtex or more. In particular, it is preferred to maintain 90% or more of the silk strength of the polylactic acid fiber before dyeing. Further, the basis weight of the fiber structure is preferably in the range of 30 to 1, 000 g/m2. Further, when the fiber structure is a woven fabric, the covering factor (CF) calculated from the following formula is 500 to 4,000 ° CF = (DWp/li) 1/2 x MWp + in terms of abrasion resistance and texture of the fiber structure. (DWf/1.1) 1/2xMWf where 'DW p is the warp total denier (dte χ ), m W p is the warp density (root / 2.54cm ) ' DWf is the weft total denier (dtex ), MWf is the weft Silk weave density (root / 2.54 cm). χ ' 13⁄4 I隹 structure is a fabric, the abrasion resistance of the fiber structure -26- 201002907 and texture, preferably 30 to 100 course number / course / 2.54 cm, 20~60 The number of needles (wale) / 2.54 cm. Such a fiber structure is dyed by using a fiber structure containing a high-melting polylactic acid fiber having a melting point of 1, 95 ° C or higher as measured by DSC, so that the fiber structure is not caused by the heat history at the time of dyeing. The fibers contained in the fibers are excessively damaged and thus exhibit excellent wear resistance. As the abrasion resistance, the planar wear resistance measured according to JIS L 1 096.8.1 7.3 C method is preferably 3 or more. Further, since the fiber structure is not hardened by heat history at the time of dyeing, the soft texture is not impaired. Of course, it is also biodegradable. The dyed fiber structure is a fiber structure which is excellent in dye fastness and has a small decrease in fiber strength in a moist heat environment. After the dyed fiber structure is treated in an environment of a temperature of 7 ° C and a humidity of 90% RH for one week, the fiber strength of the polylactic acid fiber contained in the fiber structure is preferably 0.5 cN/dtex or more, more preferably 3~10gr/dtex. In the present invention, "TENSIRON" (trade name) manufactured by ORI TEC TEC Co., Ltd. is used, and 10 target filaments (filaments) are randomly extracted from the fiber structure of the measurement object, and the length of the wire sample is 50 mm (length between the jigs). After the elongation rate is 500 mm/min, the skew-stress curve is measured under the conditions of an ambient temperature of 20 ° C and a relative humidity of 6 5 %, and the strength (cN/root) is obtained from the stress and the elongation at the time of the fracture. The intensity is divided by the fineness as the fiber strength (cN/dtex). Further, the sample was treated at 70 ° C x 90% RH for one week using a constant temperature and humidity device LHU-11 2M manufactured by tabAI ESPEC (manufacturing), and the sample was placed in an environment of the machine set in the factory set at -27-201002907 for one week. deal with. Further, the dyed fiber structure preferably has a brightness index (L値) of 80 or less. Further, the dyed fibrous structure has a washing fastness of 3 or more, which is preferably determined by the AATCC method. Further, the dyed fiber structure of the present invention may be additionally subjected to water repellent processing, raising processing, ultraviolet shielding or antibacterial agent, deodorant, insect repellent, light storing agent, retroreflective agent, negative ion generating agent, etc., using a general method. Gives a variety of processing to the function. <Fiber product> The dyed fiber structure of the present invention can be used for various fiber products. Examples of the fiber product include clothing materials, clothing materials, automobile interior materials, household goods, industrial materials, and small articles. As the clothing, for example, a shirt, a jacket, a pair of shorts, a coat, and the like are exemplified. Examples of clothing materials are overlock materials, liners, and the like. Examples of automotive interior materials include seat skins, flooring, and ceiling materials. Examples of household items are curtains, carpets, mats, cookware, and the like. Examples of industrial materials are belts, nets, ropes, heavy cloths, bags, hair consumption, and instruments. Examples of small items are clothing items, slings, glasses wiping, food wiping, tooth pads, sling toys, toy linings, hats, handbags, whiteboard cleaning cloths, notebook sheets, and the like. Since these fiber products use the dyed fiber structure of the present invention, they are not only biodegradable, but also exhibit excellent abrasion resistance and soft texture. -28- 201002907 EXAMPLES Examples and comparative examples of the present invention are described in detail below, but the present invention is not limited thereto. Further, each measurement item in the examples was measured by the following method. (1) Weight average molecular weight (Mw) The weight average molecular weight of the polymer was determined by comparison with a polystyrene standard sample by GPC (column temperature 40 ° C, chloroform). (2) Glass transfer point, melting point, and stereoscopic degree The TA-2920 differential scanning calorimeter DSC manufactured by TA Instruments was used. The measurement was carried out by heating the l〇mg sample from room temperature to 260 °C at a temperature of 1 ° C /min under a nitrogen atmosphere. The average crystal melting temperature, the glass transition temperature, and the stereoscopic compound crystal melting temperature were determined by the first scanning. The degree of stereochemistry is calculated by the following formula. S(%) = [(AHms/AHmsO)/(AHmhMHmhO + AHms/AHmsO)] X 1 00 (where ^110^0 = 203.41/^, AHmhO= 142J/g > △Hms: steric complex melting point Melting 焓, △Hmhi crystallization melting 焓) (3) Strong elongation of fiber -29- 201002907 Based on HS-L-1013, and using the constant elongation tensile test of TENSIR〇N manufactured by 〇IUENTEC The machine was measured at a clamp interval of 2 cm and a tensile speed of 20 cm/min. (4) Amount The basis weight (g/m2) was determined by JIS L 1 096. 8_5.1. (5) Abrasion resistance of fiber structure The plane wear was judged by JIS L 1 09 6. 8. 1 7_ 3 C method. Level 5 is the highest and Level 1 is the lowest. (6) Texture of the fiber structure The sensory evaluation was performed by three subjects, and it was evaluated as (grade 3) soft, and (grade 2) ordinary '(level 1) hard three grade. (7) Three-dimensional rate (Sc rate)

The X-ray diffraction pattern was recorded on a developing panel by a transmission method using a ROTA FLEX RU200B type X-ray diffraction device manufactured by Ricoh Electric Co., Ltd. under the following conditions. The diffraction intensity profile in the equatorial direction in the resulting X-ray diffraction pattern is obtained. According to the following formula, 20 = 12.0. 20.7. 24.0. The integral strength sums of the respective diffraction peaks originating from the steric complex crystals appearing near ISC1 and 2 0 = 16_5. The stereoscopic rate (Sc rate) is obtained by the integrated intensity Ihm of the diffraction peak derived from the uniform crystal which appears nearby. Also, Σ 1$£;1 and Ihm are as shown in Fig. 1, estimated by the difference between the background -30-201002907 or the scattered scattering of the diffracted intensity profile in the equator direction. X-ray source. Cu-Κα line (confocal lens) Output: 45kVx70mA Long and narrow nozzle: ΙιηηιΦ~0.8ιηηιφ Camera length: 120mm Tired I ten time: 10 minutes Sample: Length 3 cm, 35 mg Sc rate = Σ Isci/ (S Isci + lHM)xl〇〇 where Isci = lsci+Isc2 + Isc3 15 is (==1~3) is 20=12.〇. 2〇.7. 24. Integral intensity of each of the nearby diffraction peaks (8) Wash fastness was measured by the following AATCC II-A method.

1) Test method: AATCC6 1 - 1 980IIA 2) Apparatus and materials 1. Washing test machine: 40~44rpm 2·Test bottle (made of stainless steel): 45 0~550ml 3. Stainless steel ball: 0.4mm in diameter, each bottle 50 in 4. 4. Soap: solid detergent soap (JIS K3 3 02) without additives (1 kind ^ 5. sodium metasilicate (Na2Si03. 5H20) 6. glacial acetic acid 7. electric iron 8. centrifugal dehydrator or wringer -31 - 201002907 3 )Additional white cloth AATCC multi-fiber No. 1 Weft: acetate, cotton, nylon, silk, crepe, wool warp: polyester (short fiber yarn) 4) Preparation of test piece Take out a vertical lkmx The test piece of the cross-claw was sutured with 4 pieces of white cloth (multi-fiber number 1) of 5 cm x 5 cm in a manner of being in contact with the center of the test piece. In the case of braiding, a density of 80 (bar / 2 · 5 4 cm ) X 8 0 (bar / 2 _ 5 4 cm) of the same size as the test piece was used, and the test piece of 4 sides was also sewn. In order to prevent the end portion from being involved in the test, the test was carried out by placing 150 ml of 0.2% soap and 0.2% sodium metasilicate solution into the test bottle and placing 50 stainless steel hard balls. The temperature is preheated to 49. (: After that, the composite test piece was added, mounted on a closed rotating shaft and rotated for 45 minutes at a temperature of 49 T: Then, the composite test piece was taken out from the test bottle immediately after cooling without cooling to 100 ml of warm water (40 ° C) After washing for 1 minute twice, it was washed with 1 ml of water (27 ° C) for 1 minute. Then, it was dehydrated by a centrifugal dehydrator or a wringer, and the test piece and the additional white cloth were taken out at a temperature of 1 3 . 5 T: ~1 5 〇 °C electric iron pressed dry. 6) Judging the multi-fiber number 1 pollution determination, the gray part of the nylon contamination is followed by: Π SL 0 8 0 1. -32- 201002907 (5) L値 The L値 of the dyed fabric was measured for the texture of the fabric with a spectrophotometer (Gretag MacBeth Color-Eye 7000A). L値 indicates the brightness. The higher the number, the higher the brightness. The closer to 100, the lighter the color is. The closer to 0, the darker the color. (6) Fiber strength (g/dtex) In the strength of the present invention, "TENSIRON" (trade name) manufactured by ORIENTEC Co., Ltd. is used, and one single object filament (filament) is randomly drawn from the object to be measured, and the length of the wire sample is long. The skew-stress curve was measured under the conditions of an ambient gas temperature of 20 ° C and a relative humidity of 65% under conditions of 50 mm (length between clamps) and elongation speed of 500 mm/min, and the stress at the fracture point and the tensile strength (g/bar) were determined. Thereafter, the intensity is divided by the fineness as the fiber strength (g/dtex). In addition, the average enthalpy of the measurement was measured 10 times for each tether. Production Example 1 (Production of Poly L-Lactic Acid) 0.005 parts by weight of tin octylate was added to 100 parts by weight of L-lactide (manufactured by Musashi Chemical Research Institute, optical purity: 1 〇〇 ° /.) And in a reactor under a nitrogen atmosphere, placed in a reactor stirring wing, reacted at 180 ° C for 2 hours. After adding 1. 2 times equivalent of phosphoric acid relative to tin octoate, the residue was removed at 13.3 kP a. Lactide, granulated, to obtain poly-L-lactic acid. The obtained poly L-lactic acid had a weight average molecular weight of 15,000 and a glass transition point (Tg) of 63 ° C and a melting point of . -33- 201002907 Production Example 2 (Manufacturing of Poly D-Lactic Acid) Adding 0 · 0 0 to 1 part by weight of D-lactide (made by Musashi Chemical Research Institute (optical purity 1 〇 0 %) 5 parts by weight of tin octylate, and placed in a reactor equipped with stirring wings under a nitrogen atmosphere, reacted at 180 ° C for 2 hours, added with 1.2 times equivalent of phosphoric acid with tin octoate, at 1 3 _ 3 kP a to remove residual lactide, granulated to obtain poly D_lactic acid. The obtained poly D-lactic acid had a weight average molecular weight of 150,000, a glass transition point (Tg) of 63 ° C, and a melting point of 180 °C. Production Example 3 (Production of a steric miscible polylactic acid resin) 50 parts by weight of each of the poly-L-lactic acid obtained in Production Example 1 and the poly-D-lactic acid obtained in Production Example 2 and 〇_1 parts by weight of a phosphate metal salt (2,2-Methylenebis(4,6-di-tert-butylphenylhydrazine) phosphate, average particle size 5ym, ADEKASTAPU NA manufactured by ADEKA (formerly: Asahi Denki Kogyo Co., Ltd.) - 1 1 ) melt-kneading at 203t: from the first supply port, 100 parts by weight of the total of the poly-L-lactic acid and the poly-D-lactic acid is 〇.7 parts by weight as the carbodiimide CARBOZILITE LA-1 manufactured by Nisshinbo Co., Ltd., and kneaded at a cylinder temperature of 230 ° C, and the strands were taken out in a water tank and pelletized in a pelletizer to obtain a stereo-aligned polylactic acid resin. The obtained stereo-aligned polylactic acid resin had a Mw of 135,000, a melting point (Tm) of 2 17 ° C, and a stereochemistry of 100%. Production Example 4 (Production of steric miscible polylactic acid resin) The poly L-lactic acid obtained in Production Example 1 and the poly D_-34-201002907 lactic acid obtained in Production Example 2 were each 50 parts by weight and 5% by weight of phosphoric acid. The ester metal salt (ADEKASTAPU ΝΑ-ΐ 1 ) manufactured by AD ΕΚ A (share) (formerly: Asahi Denki Kogyo Co., Ltd.) is melt-kneaded at 230 ° C, and is supplied from the first supply port with respect to poly-L-lactic acid and poly 100 parts by weight of D-lactic acid is 0.7 parts by weight of CARBOZILITE LA-1 manufactured by Nisshinbo Co., Ltd. as a carbon diimide, and is kneaded at a cylinder temperature of 23 0 ° C, and the strands are taken out in a water tank. And granulated in a pelletizer to obtain a stereo-aligned polylactic acid resin. The obtained stereo-aligned polylactic acid resin had a Mw of 135,000, a melting point (Tm) of 224 ° C, and a stereoscopic ratio of 100%. Example 1 The sterically miscible polylactic acid resin obtained in the above Production Example 3 was dried at 11 (TC for 2 hours, dried at 15 ° C for 5 hours, and the water content of the resin was 80 ppm). 3 Spinning nozzle of 6 hole diameter 〇· 2 7 mm discharge hole, after spinning at a spinning temperature of 25 5 °C at a spinning rate of 8.3 5 g/min, coiling at a speed of 500 m/min The wire is not stretched. The unstretched wire taken up is extended by 490 times on the stretcher at 80 ° C, and the stretched wire is taken up, and then heat-treated at 180 ° C. The steps in the spinning step and the stretching step are good. The stretched wire is a multi-fiber with a fineness of 167dTex/36fil, the strength is 3.6 cN/dTex, the elongation is 35%, and the melting point is 213 ° C. The two obtained stereoscopically misaligned polylactic acid fibers are combined and subjected to 1 60 Τ/ After 捻 捻 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Dyeing was carried out for 20 minutes at C. At this time, the dye was dispersed using -35-201002907. Then, via the impregnation winch The fiber structure was subjected to drying at a temperature of 130 ° C for 1 minute and then dried at a temperature of 160 ° C for 2 minutes. The resulting fabric was warp. Density 4 * strip / cm, weft density 1 8 / cm, coverage factor 2 6 9 0, flat wear level 3, texture level 3 'and wear resistance and soft texture. Next, use the fabric sewing The surface material of the vehicle seat (automobile interior material). The vehicle seat surface material is a wear-resistant and soft texture. Embodiment 2 Only the stereo-aligned polylactic acid fiber obtained in Example 1 is used.捻 丝 ( (1 60 T/m ) 'Use a 20 knitting machine to make a circular braid of 1 mesh mesh. Then, let the braid dry and heat for 2 minutes at 150 °C. Thereafter, the liquid dyeing machine was used to perform dyeing at a temperature of 120 ° C for 20 minutes. At this time, a disperse dye was used. Moreover, the fiber structure was given a weight relative to the fiber structure by an impregnation winch machine. 1 · 5 wt% of bismuth resin, and dried at a temperature of 130 ° C for 10 minutes After 'at a temperature of 16 〇. (:: apply dry heat setting for 2 minutes. The resulting fabric is a warp density of 3 5 rows of needles / 2 · 5 4 cm, weft density of 24 / 2.54 cm, plane wearability 3 Grade, texture level 3, and exhibits wear resistance and soft texture. Then 'Use this fabric to sew the skin material of the car seat (automobile interior material). The car seat skin material shows wear resistance. -36-201002907 Comparative Example 1 In Example 1, except that the poly-L-lactic acid obtained in Production Example 1 was used instead of the sterically miscible polylactic acid, the remainder was the same as in Example 1. The polylactic acid fiber has a melting point of 1 80 °C. The resulting fabric shrinks and hardens due to the heat experienced during dyeing (texture level 1). In addition, it is a flat wear level and a poor wear resistance. Reference Example 1 In addition to 0.5 parts by weight of aluminum bis(2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate) hydroxide (ADEKA (share) (original: Asahi) ADEKASTAPU NA-21 manufactured by Electrochemical Industry Co., Ltd.) As the phosphate metal salt, the operation was carried out in the same manner as in Example 1, and a sharp sublimate was generated during spinning, which was difficult to spin. Example 3 The sterically miscible polylactic acid resin obtained in Production Example 4 was dried at 110 ° C for 2 hours, and dried at 15 ° C for 5 hours to have a water content of the resin of 80 ppm. A spinning nozzle of a 36-hole diameter 27.27 mm spout hole is spun at a spinning temperature of 2 5 5 ° C at a spinning rate of 8.3 5 g/min, and the undrawn yarn is taken up at a speed of 500 m/min. . The unstretched filaments which were taken up were preheated at 80 ° C on a stretching machine for 4 · 9 times to take up the stretched yarn, and then heat-treated at 180 ° C. The spinning step and the step in the stretching step have good passability, and the drawn filament is a multifilament of 167dTex/36fil, the strength is 3.6 -37-201002907 cN/dTex, the elongation is 35%, and the single melting peak is determined by DSC. The dissolution peak temperature (melting point) was 224 ° C. The stereochemistry rate was 100%. Two pieces of the obtained three-dimensionally misaligned polylactic acid fiber were twisted, and after twisting of 160 K/m, and then arranged into a warp and weft yarn to fabricate a twill weave fabric, the fabric was made at 150 °C. After 2 minutes of dry heat setting at the temperature, the dyeing was carried out for 30 minutes at a temperature of 12 ° C using a liquid flow dyeing machine. At this time, the following disperse dye was used for dyeing, and a reduction washing treatment was carried out. (Disperse dye name) C. I. Disperse Blue 79 1 % owf Wash the obtained dye in the following reduction bath (pH 5.5): bath ratio; 1: 2 0 temperature X time; 12 (TC X 30 minute reduction bath Composition and washing conditions: sulfur dioxide urea lg/L bath ratio; 1: 2 0 temperature X time; 70 ° C x l 5 minutes, then drying at a temperature of 130 ° C for 10 minutes, drying at a temperature of 160 ° C 2 minutes. After the treatment, in the dyed fiber structure, the L値 is 38, the washing fastness is 4, and the sterically miscible lactic acid fiber contained in the woven material is treated at 70 °C X 90% RH. The fiber strength after the week was 1·8 cN/dtex (300 g/bar). Then, the woven material was used to obtain a uniform clothing, which was excellent in fastness to washing and good in durability. -38 - 201002907 Example 4 Example 3 In the above, except that the content of the phosphate metal salt was changed to a part by weight, the remainder was the same as in Example 3. The obtained dyed fiber structure was 3, and the washing fastness was 4, and the woven material contained three-dimensional. The fiber strength of the mismatched lactic acid fiber after treatment at 70 ° C x 90% RH for 1 week was 1.8 cN / dtex (300 g / strip Then, the woven material was used to obtain a uniform fabric, which was excellent in washing fastness and durability. Example 5 In Example 3, except that the content of the phosphate metal salt was changed to parts by weight, the remainder was the same as in Example 3. The obtained dyed fiber structure has an L値 of 38, and the washing fastness is 4, and the fiber density of the sterically miscible lactic acid fiber contained in the woven material is treated at 70 ° C x 90% RH for 1 week. cN/dtex (3 00 g/bar). Then, the woven material was used to obtain a uniform clothing, which was excellent in washing fastness and good in durability. Comparative Example 2 In Example 3, except that sterically miscible polylactic acid was used instead of Production Example 1 The obtained poly L-lactic acid was the same as in Example 3. The stretched yarn had a single melting peak as determined by DSC, and the melting peak temperature (melting point) was 180 ° C. The obtained fabric was 70 ° C x 9 0% RH. After 1 week of treatment, the fiber strength was 0.05 cN/dtex (8 g/strand), and it was difficult to maintain the structure of the fabric. Effect of the invention-39-201002907 According to the present invention, it is possible to obtain not only a biodegradable twin, but also a soft texture and wear resistance. Excellent in both consumption and washing fastness Dyeing IMtl Body 0 Industrial Applicability The dyed fiber structure of the present invention can be used as a raw material for fabrics, textile materials, automobile interior materials, household products, industrial materials, and the like. Brief Description of the Formula] Figure 1 shows the diffraction intensity profile of the equatorial direction for obtaining the stereoscopic rate (Sc rate).

Claims (1)

201002907 X. Patent application scope 1. A method for producing a dyed fiber structure, characterized in that a fiber structure comprising a polylactic acid fiber having a melting point of 1 95 ° C or more is dyed. 2. The manufacturing method according to claim 1, wherein the polylactic acid fiber contains (i) a poly-L-lactic acid (component A) having a weight average molecular weight of 50,000 to 300,000, and a weight average molecular weight of 50,000 to 30. D-lactic acid (B component) and (iii) 1 part by weight of each a component and B component, and 0.05 to 5 parts by weight of a phosphate metal represented by the following formula (1) or (2) salt: (1) In the formula (1), R! represents a hydrogen atom or a group of carbon atoms 1 to 4', and R3 each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and Μ! represents an alkali metal atom or an alkaline earth. Metal-like atom, Ρ means 1 or 2, 201002907 (2) In the formula (2), R4, R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, M2 represents an alkali metal atom or an alkaline earth metal atom, and P represents 1 or 2 〇3. The manufacturing method of the first aspect of the invention, wherein the polylactic acid fiber contains 0.1 to 5 parts by weight of a carbodiimide compound per 1 part by weight of the total of the poly-L-lactic acid component and the poly-D-lactic acid component, and The molecular weight retention after treatment in high temperature water at 130 ° C for 30 minutes was 85% or more. 4. The manufacturing method according to claim 1, wherein the polyfilament fiber has a single filament fineness in the range of 0.01 to 20 dtex. 5. The manufacturing method of claim 1, wherein the poly% _ Μ silk has a strength of 2.5 cN/dtex or more. 6. The manufacturing method of claim 1, wherein the fiber structure contains other fibers. 7. The manufacturing method as claimed in claim 6 wherein the other fibers are polyethylene terephthalate fibers. 8. The manufacturing method of claim i, wherein the fibrous structure is a fabric or a knitted fabric. 9. The method of manufacturing the invention of claim 2, wherein the dyeing temperature is in the range of 110 to 140 °C. The manufacturing method of claim 1, wherein the reduction washing treatment is carried out after the dyeing treatment. 1 1 The manufacturing method of claim 10, wherein the reduction washing treatment is carried out in a reduction bath having a pH of 8 to 2 at a temperature of 60 to 98. (2) The method according to the first aspect of the invention, wherein after the dyeing, a resin, a polyethylene resin or a polyethylene terephthalate resin is imparted to the fiber structure. 13. A dyed fibrous structure produced by the manufacturing method of any one of claims 1 to 12. 1 4 - a fibrous structure according to claim 13 of the patent application, wherein The fiber strength of the polylactic acid fiber contained in the fiber structure is 2.3 cN/dteX or more 〇1 5 _ as in the fiber structure of the third aspect of the patent application, wherein the temperature is 70 ° C and the humidity is 90% rh After one week of treatment, the fiber strength of the polylactic acid fiber contained in the fiber structure is 0.5 cN/dtex or more. 16. The fiber structure of the third aspect of the patent application has a basis weight of 30 to 1,000 g. Fabrics in the range of /m2. 1 7 · If the fiber structure of the third paragraph of the patent application is applied, the plane wearability is a fabric of grade 3 or higher. 1 8 If the fiber structure of the third paragraph of the patent application is applied, Its brightness index (L値) is below 80. The fiber structure of the third aspect of the patent, which has a washing fastness of 3 or more by the AATCC IIA method. -43- 201002907 2 0, a fibrous product selected from the scope of application patents. Group of clothing materials, clothing materials, automotive interior materials, household products, industrial materials and small items consisting of dyed fiber structures of any of the items.