JP2010222714A - Fabrics and dyed fabrics and textile products - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fabric that not only exhibits a soft touch characteristic of ultrafine fiber but has excellent color development and color fastness, high fabric strength and slight environmental load; a dyed fabric obtained by dyeing the fabric; and a fiber product using the dyed fabric. <P>SOLUTION: The fabric comprises a polyester filament yarn A having a single filament diameter of 10-1,000 nm and a normal-pressure cation dyeable filament yarn B having a single filament diameter of >1,000 nm. Preferably the number of filaments of the polyester filament yarn A is ≥500. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a fabric, a dyed fabric and a textile product which not only exhibit a soft texture peculiar to ultrafine fibers but also have excellent color developability and dyeing fastness, high fabric strength, and low environmental load.

Conventionally, ultra-fine fibers called nanofibers have been developed extensively in the fields of apparel use, inner apparel, sports apparel, etc. in order to exhibit the soft texture unique to ultra-fine fibers (for example, patent documents) 1, Patent Document 2, Patent Document 3, and Patent Document 4).
However, although the ultrafine fiber has a small fiber diameter, it has a problem that although it absorbs the dye, it has poor color developability, and the dyeing fastness is not sufficient (see, for example, Patent Document 5, Patent Document 6, and Patent Document 7). ).

  In addition, in the Japanese Patent Application No. 2008-215207, the present applicant obtained a fabric using a normal pressure cationic dyeable fiber, and then dyed the fabric with a cationic dye, whereby excellent color developability and dyeing fastness. It is proposed to obtain a dyed fabric having high fabric strength and low environmental load. In addition, in Japanese Patent Application No. 2008-056188, the present applicant obtains a fabric using ultrafine fibers and ordinary cationic dyeable fibers, and then dyes the fabric with a cationic dye to obtain ultrafine fibers. We have proposed dyed fabrics that not only exhibit the soft texture unique to fibers but also have excellent color development and dyeing fastness.

JP 2003-41432 A JP 2004-162244 A JP-A-2005-23466 JP 2007-2364 A JP 2007-303020 A Japanese Patent Laid-Open No. 5-331784 JP 60-34671 A

  The present invention has been made in view of the above background, and its purpose is not only to exhibit a soft texture peculiar to ultrafine fibers, but also to have excellent color developability and dyeing fastness, high fabric strength, It is an object of the present invention to provide a fabric having a low environmental load, a dyed fabric obtained by dyeing the fabric, and a fiber product using the dyed fabric.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained a fabric using ultrafine fibers having a single fiber diameter of 1000 nm or less and atmospheric pressure cationic dyeable fibers having a single fiber diameter of more than 1000 nm. Thereafter, the fabric is dyed at normal pressure with a cationic dye, so that it not only exhibits a soft texture peculiar to ultrafine fibers, but also has excellent color development and dyeing fastness, and the fabric strength is high. The present inventors have found that a dyed fabric that is high and has a low environmental load can be obtained, and have further studied earnestly to complete the present invention.

  Thus, according to the present invention, there is provided a “fabric comprising the polyester filament yarn A having a single fiber diameter of 10 to 1000 nm and the normal pressure cationic dyeable filament yarn B having a single fiber diameter of 1000 nm”. The

  At that time, the number of filaments of the polyester filament yarn A is preferably 500 or more. Further, the polyester filament yarn A is preferably a yarn obtained by dissolving and removing the sea component of the sea-island type composite fiber composed of the sea component and the island component. Further, the normal pressure cationic dyeable filament yarn B is made of a copolymerized polyester fiber, and the copolymerized polyester fiber is used as a copolymerization component in a metal salt of sulfoisophthalic acid (A) and the following formula ( Containing the compound (B) represented by I) so as to satisfy the following mathematical formulas (1) and (2) at the same time, and the glass transition temperature of the copolyester is in the range of 70 to 85 ° C., and It is preferable that the copolyester fiber is a copolyester fiber made of a copolyester having an intrinsic viscosity of 0.55 to 1.00 dL / g.

［上記式中、Ｒは水素原子又は炭素数１〜１０個のアルキル基を表し、Ｘは４級ホスホニ
ウムイオン又は４級アンモニウムイオンを表す。］
３．０≦Ａ＋Ｂ≦５．０ （１）
０．２≦Ｂ／（Ａ＋Ｂ）≦０．７ （２）
［上記数式中、Ａは共重合ポリエステルを構成する全酸成分を基準とするスルホイソフタ
ル酸の金属塩（Ａ）の共重合量（モル％）、Ｂは共重合ポリエステルを構成する全酸成分
を基準とする上記式（Ｉ）で表される化合物（Ｂ）の共重合量（モル％）を表す。］

[In the above formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents a quaternary phosphonium ion or a quaternary ammonium ion. ]
3.0 ≦ A + B ≦ 5.0 (1)
0.2 ≦ B / (A + B) ≦ 0.7 (2)
[In the above formula, A is the copolymerization amount (mol%) of the metal salt of sulfoisophthalic acid (A) based on the total acid component constituting the copolyester, and B is the total acid component constituting the copolyester. This represents the copolymerization amount (mol%) of the compound (B) represented by the above formula (I) as a reference. ]

  In the present invention, the fabric is preferably a woven fabric, and the polyester filament yarn A and the cationic dyeable filament yarn B are regularly included in the warp and / or weft of the woven fabric. Moreover, it is preferable that the fabric is a woven fabric, in which one of the warp and weft of the woven fabric contains the polyester filament yarn A, and the other contains the cationic dyeable filament yarn B. The fabric is a multilayer fabric having a multilayer structure of two or more layers, wherein the polyester filament yarn A is included in at least one layer, and the cationic dyeable filament yarn B is included in the other layer. Is preferred. In particular, it is preferable that the fabric has a multilayer structure of three or more layers, the outermost layer or the innermost layer includes the polyester filament yarn A, and the other layer includes the cationic dyeable filament yarn B. Further, the fabric includes the polyester filament yarn A and the atmospheric pressure cationic dyeable filament yarn B, and the polyester filament yarn A and / or the cationic dyeable filament yarn B is included in the fabric as a part of the composite yarn. Is preferred. In this case, the composite yarn is preferably any one selected from the group consisting of an air mixed yarn, a composite false twist crimped yarn, and a covering yarn.

  In addition, according to the present invention, there is provided a dyed fabric obtained by dyeing the above fabric with a cationic dye. In such a dyed fabric, the lightness L value is preferably 40 or less. Moreover, it is preferable that the wash dyeing fastness measured by JIS L0844 is 3rd grade or more. Moreover, it is preferable that the fastness to friction dyeing measured by JIS L0849 is 3rd grade or more.

  Further, according to the present invention, sportswear, outdoor wear, raincoat, umbrella, men's clothing, women's clothing, work clothing, protective clothing, artificial leather, footwear, heels, curtains, comprising the dyed fabric described above, Any fiber product selected from the group of waterproof sheets, tents, and car seats is provided.

  According to the present invention, not only the soft texture peculiar to ultra-fine fibers but also excellent color developability and dyeing fastness, high fabric strength, low environmental impact, and dyeing the fabric. A dyed fabric and a fiber product using the dyed fabric are obtained.

Hereinafter, embodiments of the present invention will be described in detail.
First, it is important that the polyester filament yarn A used in the present invention has a single fiber diameter (single fiber diameter) of 10 to 1000 nm (preferably 100 to 800 nm, particularly preferably 550 to 800 nm). When this single fiber diameter is converted into a single yarn fineness, it corresponds to 0.000001 to 0.01 dtex. When the single fiber diameter exceeds 1000 nm, the dyed fabric does not exhibit a soft texture peculiar to ultrafine fibers, which is not preferable. On the other hand, when the single fiber diameter is less than 10 nm, the fiber strength is lowered, which is not preferable for practical use. Here, when the cross-sectional shape of the single fiber is an atypical cross section other than the round cross section, the diameter of the circumscribed circle is defined as the single fiber diameter. The single fiber diameter can be measured by photographing the cross section of the fiber with a transmission electron microscope.

  In the polyester filament yarn A, the number of filaments is not particularly limited, but it is preferably 500 or more (more preferably 2000 to 10,000) in order to obtain a texture peculiar to ultrafine fibers. The total fineness of the polyester filament yarn A (the product of the single fiber fineness and the number of filaments) is preferably in the range of 5 to 150 dtex.

  The fiber form of the polyester filament yarn A is not particularly limited, but is preferably a long fiber (multifilament yarn). The cross-sectional shape of the single fiber is not particularly limited, and may be a known cross-sectional shape such as a circle, a triangle, a flat shape, or a hollow shape. In addition, normal air processing and false twist crimping may be applied.

  The polyester forming the polyester filament yarn A is produced from a dicarboxylic acid component and a diglycol component. As the dicarboxylic acid component, terephthalic acid is preferably used mainly, and as the diglycol component, it is preferable to use one or more alkylene glycols selected from ethylene glycol, trimethylene glycol and tetramethylene glycol. Further, the polyester may contain a third component in addition to the dicarboxylic acid component and the glycol component. Examples of the third component include cationic dye dyeable anion components such as sodium sulfoisophthalic acid; dicarboxylic acids other than terephthalic acid such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid; and glycol compounds other than alkylene glycol. For example, one or more of diethylene glycol, polyethylene glycol, bisphenol A, and bisphenol sulfone can be used. Such polyester may be biodegradable polyester such as polylactic acid, material recycled or chemically recycled polyester. Moreover, the polyester obtained using the catalyst containing the specific phosphorus compound and titanium compound which are described in Unexamined-Japanese-Patent No. 2004-270097 and 2004-21268 may be sufficient. Furthermore, aliphatic polyesters such as polylactic acid and stereocomplex polylactic acid may be used. In the polyester polymer, a fine pore forming agent, a cationic dye dyeing agent, an anti-coloring agent, a heat stabilizer, a fluorescent whitening agent, a matting agent, as necessary within the range not impairing the object of the present invention, One or two or more colorants, hygroscopic agents, and inorganic fine particles may be contained.

  Further, the polyester filament yarn A is preferably a yarn obtained by dissolving and removing the sea component of the sea-island type composite fiber composed of the sea component and the island component. For example, first, the following sea component polymer and island component polymer for sea-island type composite fibers are prepared.

  The sea component polymer may be any polymer as long as the dissolution rate ratio with respect to the island component is 200 or more, but polyesters, polyamides, polystyrenes, polyethylenes, and the like having good fiber forming properties are particularly preferable. For example, as an easily soluble polymer in an alkaline aqueous solution, polylactic acid, an ultra-high molecular weight polyalkylene oxide condensation polymer, a polyethylene glycol compound copolymer polyester, a copolymer polyester of polyethylene glycol compound and 5-sodium sulfonic acid isophthalic acid may be used. Is preferred. Nylon 6 is soluble in formic acid, and polystyrene and polyethylene are very well soluble in organic solvents such as toluene. Among them, in order to achieve both easy alkali solubility and sea-island cross-section formability, the polyester-based polymer is 3 to 10% by weight of polyethylene glycol having 6 to 12 mol% of 5-sodium sulfoisophthalic acid and a molecular weight of 4000 to 12000. % Copolymerized polyethylene terephthalate copolymer polyester having an intrinsic viscosity of 0.4 to 0.6 is preferred. Here, 5-sodium isophthalic acid contributes to improving hydrophilicity and melt viscosity, and polyethylene glycol (PEG) improves hydrophilicity. PEG has a higher hydrophilicity effect, which is thought to be due to its higher order structure, as the molecular weight increases, but it is preferable from the viewpoints of heat resistance and spinning stability because the reactivity becomes poor and a blend system is formed. Disappear. On the other hand, when the copolymerization amount is 10% by weight or more, it is difficult to achieve the object of the present invention because of its inherently low melt viscosity. Therefore, it is preferable to copolymerize both components within the above range.

  On the other hand, the island component polymer may be any polyester polymer as long as it has a difference in dissolution rate from the sea component. However, as described above, fiber-forming polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, stereocomplex poly Polyester such as lactic acid, polylactic acid, polyester obtained by copolymerizing the third component is preferred.

  The sea-island composite fiber composed of the sea component polymer and the island component polymer preferably has a sea component melt viscosity higher than that of the island component polymer during melt spinning. In such a relationship, even if the composite weight ratio of the sea component is less than 40%, the islands are joined together, or the majority of the island components are joined to be different from the sea-island type composite fiber. hard.

  A preferred melt viscosity ratio (sea / island) is in the range of 1.1 to 2.0, especially 1.3 to 1.5. If this ratio is less than 1.1 times, the island components are likely to be joined during melt spinning, whereas if it exceeds 2.0 times, the viscosity difference is too large and the spinning tone tends to be lowered.

  The number of islands is preferably 100 or more (more preferably 300 to 1000) because the productivity in the case of producing ultrafine fibers by dissolving and removing sea components increases as the number of islands increases. If the number of islands is too large, not only the manufacturing cost of the spinneret increases, but also the processing accuracy itself tends to decrease.

  Next, the diameter (diameter) of the island component needs to be in the range of 10 to 1000 nm (preferably 100 to 800 nm). By setting the diameter of the island component within the range, the finally obtained woven fabric includes a multifilament yarn having a single fiber diameter (single fiber diameter) of 10 to 1000 nm. Here, when the cross-sectional shape of the island component is an atypical cross-section other than the round cross-section, the diameter of the circumscribed circle is the diameter of the island component. In addition, the diameter (diameter) of the island component can be measured by dissolving and removing the sea component of the sea-island type composite fiber with an alkaline aqueous solution and then photographing the cross section of the fiber with a transmission electron microscope.

  As the spinneret used for melt spinning, any one such as a hollow pin group for forming an island component or a group having a fine hole group can be used. For example, any spinneret that forms a cross section of the sea island by joining the island component extruded from the hollow pin or the fine hole and the sea component flow designed to fill the gap between the sea component flow may be used. .

  The discharged sea-island type cross-section composite fiber is solidified by cooling air, and is preferably wound after being melt-spun at 400 to 6000 m / min. The obtained undrawn yarn is made into a composite fiber having desired strength, elongation, and heat shrinkage properties through a separate drawing process, or is taken up by a roller at a constant speed without being wound once, and subsequently drawn. Any of the methods of winding after passing through may be used.

  Here, in order to produce a sea-island type composite fiber having a particularly fine island diameter with high efficiency, the fiber structure is not changed prior to neck stretching (orientation crystallization stretching) with ordinary so-called orientation crystallization. It is preferable to employ a fluid stretching process in which only the diameter is extremely reduced. In order to facilitate fluid drawing, it is preferable to preheat the fiber uniformly using an aqueous medium having a large heat capacity and draw at a low speed. By doing so, it becomes easy to form a fluid state at the time of stretching, and it can be easily stretched without development of the fine structure of the fiber. In this process, both the sea component and the island component are preferably polymers having a glass transition temperature of 100 ° C. or less, and particularly suitable for polyesters such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid, and polytrimethylene terephthalate. Specifically, it is immersed in a hot water bath in the range of 60 to 100 ° C., preferably 60 to 80 ° C., and uniformly heated, the draw ratio is 10 to 30 times, the supply speed is 1 to 10 m / min, and the winding speed is It is preferable to carry out in the range of 300 m / min or less, particularly 10 to 300 m / min. If the preheating temperature is insufficient and the stretching speed is too fast, high-strength stretching cannot be achieved.

  The drawn yarn drawn in the fluidized state is oriented, crystallized and drawn at a temperature of 60 to 220 ° C. in accordance with a conventional method in order to improve mechanical properties such as the strength and elongation. If the drawing conditions are outside this range, the properties of the resulting fiber will be insufficient. The draw ratio varies depending on the melt spinning conditions, flow stretching conditions, orientation crystallization stretching conditions, etc., but is 0.6 to 0.95 times the maximum draw ratio that can be stretched under the orientation crystallization stretching conditions. What is necessary is just to extend | stretch.

  In the sea-island type composite fiber thus obtained, the sea-island composite weight ratio (sea: island) is preferably in the range of 40:60 to 5:95, and particularly preferably in the range of 30:70 to 10:90. Within such a range, the thickness of the sea component between the islands can be reduced, the sea component can be easily dissolved and removed, and the conversion of the island component into ultrafine fibers is facilitated. Here, when the proportion of the sea component exceeds 40%, the thickness of the sea component becomes too thick. On the other hand, when the proportion is less than 5%, the amount of the sea component becomes too small, and joining between the islands easily occurs.

  In the sea-island type composite fiber, the thickness of the sea component between the islands is 500 nm or less, particularly 20 to 200 nm, and when the thickness exceeds 500 nm, the thick sea component is dissolved and removed. In addition, since the island components are dissolved, not only the homogeneity between the island components is lowered, but also defects such as fuzz and pilling and dyeing spots are likely to occur.

  Next, the sea-island type composite fiber is subjected to an alkaline aqueous solution treatment, and sea components of the sea-island type composite fiber are dissolved and removed with an alkaline aqueous solution, whereby the sea-island type composite fiber filament yarn is a polyester filament yarn A having a single fiber diameter of 10 to 1000 nm. And At that time, the alkaline aqueous solution treatment may be performed at a temperature of 55 to 65 ° C. using a 3 to 4% NaOH aqueous solution. The alkaline aqueous solution treatment may be performed before weaving the fabric, but is preferably performed after weaving the fabric.

  On the other hand, it is important that the normal pressure cationic dyeable filament yarn B has a single fiber diameter larger than 1000 nm (1 μm) (preferably 1.1 to 20 μm). When the single fiber diameter is 1000 nm or less, although the single fiber diameter becomes too thin and the dye is exhausted, it is not preferable because excellent color developability cannot be obtained. On the other hand, if the single fiber diameter is larger than 20 μm, the peach touch-like unique texture of the ultrafine fibers may be impaired. Here, when the cross-sectional shape of the single fiber is an atypical cross section other than the round cross section, the diameter of the circumscribed circle is defined as the single fiber diameter. The single fiber diameter can be measured by photographing the cross section of the fiber with a transmission electron microscope, as described above.

  In the polyester filament yarn B, the number of filaments is not particularly limited, but is preferably in the range of 1 to 300. The fiber form of the polyester filament yarn B is not particularly limited, but is preferably a long fiber (multifilament yarn). The cross-sectional shape of the single fiber is not particularly limited, and may be a known cross-sectional shape such as a circle, a triangle, a flat shape, or a hollow shape. In addition, normal air processing and false twist crimping may be applied.

  The type of the polymer that forms the normal pressure cationic dyeable filament yarn B is not particularly limited as long as it is an atmospheric pressure cationic dyeable polymer, but the following copolymer polyester (hereinafter simply referred to as “copolyester”): Is sometimes preferred).

  The normal pressure cationic dyeable filament yarn referred to in the present invention is CATILON BLUE CD-FRLH) 0.2 g / L, CD-FBLH 0.2 g / L (both are cation dyeable by Hodogaya Chemical Co., Ltd.) Dye), sodium sulfate 3 g / L, acetic acid 0.3 g / L in a dyeing solution at 100 ° C. (normal pressure) for 1 hour at a bath ratio of 1:50, Macbeth Color Eye (Macbeth COLOR) EYE) is a filament yarn that uses model M 2020PL and has a lightness L value of 40 or less represented by L * a * b * system color display defined in JISZ 8729-1980.

  The copolymer polyester is a copolymer polyester having ethylene terephthalate as a main repeating unit obtained by polycondensation reaction of terephthalic acid or an ester-forming derivative thereof and an ethylene glycol component, and sulfoisophthalic acid as a copolymer component. A copolyester containing the metal salt (A) of the above and the compound (B) represented by the following formula (I) in a state satisfying the following formulas (1) and (2) simultaneously, The polyester is characterized in that the transition temperature is in the range of 70 to 85 ° C., and the intrinsic viscosity of the resulting copolyester is in the range of 0.55 to 1.00 dL / g.

［上記式中、Ｒは水素又は炭素数１〜１０個のアルキル基を表し、Ｘは４級ホスホニウム
塩又は４級アンモニウム塩を表す。］
３．０≦Ａ＋Ｂ≦５．０ （１）
０．２≦Ｂ／（Ａ＋Ｂ）≦０．７ （２）
［上記数式中、Ａは共重合ポリエステルを構成する全酸成分を基準とするスルホイソフタル酸の金属塩（Ａ）の共重合量（モル％）、Ｂは共重合ポリエステルを構成する全酸成分を基準とする上記式（Ｉ）で表される化合物（Ｂ）の共重合量（モル％）を表す。］

[In the above formula, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and X represents a quaternary phosphonium salt or a quaternary ammonium salt. ]
3.0 ≦ A + B ≦ 5.0 (1)
0.2 ≦ B / (A + B) ≦ 0.7 (2)
[In the above formula, A is the copolymerization amount (mol%) of the metal salt of sulfoisophthalic acid (A) based on the total acid component constituting the copolyester, and B is the total acid component constituting the copolyester. This represents the copolymerization amount (mol%) of the compound (B) represented by the above formula (I) as a reference. ]

  Here, the ester-forming derivative of terephthalic acid is dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester, dioctyl ester, didecyl ester, or diphenyl ester or terephthalic acid dichloride, terephthalic acid diester. Among them, dimethyl terephthalate is preferable.

(About copolymer polyester)
The copolymer polyester is a polyester having ethylene terephthalate as a main repeating unit, and the main repeating unit indicates that 80 mol% or more of all repeating units constituting the copolymer polyester is an ethylene terephthalate unit. Other components may be copolymerized within the other 20 mol% or less range. Preferably 90 mol% or more is an ethylene terephthalate unit. Other copolymer components include diphthalic acid components such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, diphenyl Examples thereof include ketone dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, succinic acid, adipic acid, and azelaic acid, and 1,2-propylene glycol, trimethylene glycol, tetramethylene glycol, heptamethylene glycol, Hexamethylene glycol, diethylene glycol, dipropylene glycol, bis (trimethylene glycol), bis (tetramethylene glycol), triethylene glycol, 1,4-dihydroxycyclohexane, 1,4-cyclohexa Can dimethanol mentioned, it may be copolymerized as a repeating unit derived ingredients by reacting these one or more dicarboxylic acids and one or more glycol components.

(About metal salt of sulfoisophthalic acid (A))
Examples of the metal salt (A) of sulfoisophthalic acid to be used include alkali metal salts (lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt) of 5-sulfoisophthalic acid. If necessary, alkaline earth salts such as magnesium salts and calcium salts of these compounds may be used in combination. These ester-forming derivatives are also preferably exemplified. Examples of the ester-forming derivatives include dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester, dioctyl ester, didecyl ester, diphenyl ester, and dihalogenated metal salt of 5-sulfoisophthalic acid. Of these, dimethyl ester is preferred. Among these compounds, an alkali metal salt of 5-sulfoisophthalic acid is preferably exemplified from the viewpoint of thermal stability, cost, etc., and in particular, 5-sodium sulfoisophthalic acid which is 5-sodium sulfoisophthalic acid or a dimethyl ester thereof. Particularly preferred is dimethyl acid. In the case of a compound satisfying these conditions, it is possible to achieve both sufficient cationic dyeability and sufficient fiber strength when used as a polyester fiber.

(Compound (B))
The compound (B) represented by the above formula (I) is quaternary phosphonium salt or quaternary ammonium salt of 5-sulfoisophthalic acid or a lower alkyl ester thereof. As the quaternary phosphonium salt or quaternary ammonium salt, a quaternary phosphonium salt or a quaternary ammonium salt in which an alkyl group, a benzyl group or a phenyl group is bonded to a phosphorus atom or a nitrogen atom is preferable, and a quaternary phosphonium salt is particularly preferable. preferable. The four substituents may be the same or different. Specific examples of the compound represented by the above formula (I) include 5-sulfoisophthalic acid tetrabutylphosphonium salt, 5-sulfoisophthalic acid ethyltributylphosphonium salt, 5-sulfoisophthalic acid benzyltributylphosphonium salt, and 5-sulfoisophthalic acid. Acid phenyltributylphosphonium salt, 5-sulfoisophthalic acid tetraphenylphosphonium salt, 5-sulfoisophthalic acid butyltriphenylphosphonium salt, 5-sulfoisophthalic acid benzyltriphenylphosphonium salt, 5-sulfoisophthalic acid tetramethylammonium salt, 5- Sulfoisophthalic acid tetraethylammonium salt, 5-sulfoisophthalic acid tetrabutylammonium salt, 5-sulfoisophthalic acid tetraphenylammonium salt, 5-sulfoisophthalic acid benzyl trime Le ammonium salt, 5-sulfoisophthalic acid benzyl trimethyl ammonium salt, or dimethyl esters thereof isophthalic acid derivatives, the diethyl ester, dipropionate pull ester, dibutyl ester, hexyl ester to di, dioctyl ester, didecyl ester is preferably exemplified. Among these isophthalic acid derivatives, 5-sulfoisophthalic acid dimethyltetrabutylphosphonium salt, 5-sulfoisophthalic acid dimethylbenzyltributylphosphonium salt, 5-sulfoisophthalic acid dimethyltetraphenylphosphonium salt, 5-sulfoisophthalic acid dimethyltetramethylammonium salt More preferred examples include salts, dimethyltetraethylammonium salt of 5-sulfoisophthalic acid, dimethyltetrabutylammonium salt of 5-sulfoisophthalic acid, and dimethylbenzyltrimethylammonium salt of 5-sulfoisophthalic acid. In the case of a compound satisfying these conditions, it is possible to achieve both sufficient cationic dyeability and sufficient fiber strength when used as a polyester fiber.

(About Formula (1))
The total of the metal salt (A) of the sulfoisophthalic acid to be copolymerized with the polyester and the compound (B) is the sum of the components (A) and (B) based on the total acid components constituting the copolymerized polyester. A + B needs to be in the range of 3.0 to 5.0 mol%. If it is less than 3.0 mol%, sufficient dyeing cannot be obtained by cationic dyeing under normal pressure. On the other hand, if it exceeds 5.0 mol%, the strength of the resulting polyester yarn is lowered, which is not suitable for practical use. Further, since the dye is consumed excessively, it is disadvantageous in terms of cost. Preferably it is 3.2-4.8 mol%, More preferably, it is 3.3-4.7 mol%.

(About Formula (2))
Further, the component ratio of the metal salt (A) of sulfoisophthalic acid and the compound (B) needs to be in the range of 0.2 to 0.7, with B / (A + B) being the value of the above mol%. When the ratio is 0.2 or less, that is, the ratio of component A is large, it is difficult to increase the degree of polymerization of the resulting copolyester due to the thickening effect of the metal salt of sulfoisophthalic acid. On the other hand, when the ratio of the compound (B) is 0.7 or more, that is, the polycondensation reaction is slow, and when the ratio of the compound (B) is further increased, it is difficult to increase the degree of polymerization because the thermal decomposition reaction proceeds. Become. Furthermore, when the ratio of the compound (B) increases, the thermal stability of the copolyester deteriorates, and the decrease in the molecular weight due to the thermal decomposition reaction upon remelting at the melt spinning stage increases, so the strength of the resulting polyester yarn decreases. Therefore, it is not preferable. Preferably it is 0.23-0.65, More preferably, it is 0.00.
25 to 0.60.

  Although cationic dyeability can be imparted by copolymerizing a metal salt of sulfoisophthalic acid (A) with polyester, an increase in the melt viscosity of the copolymerized polyester that is thought to be derived from ionic bonds between the metal sulfonate groups. It was difficult to increase the degree of polymerization of the copolyester due to the viscous effect. Therefore, a copolyester having a sufficiently high degree of polymerization and a high intrinsic viscosity cannot be obtained, and the polyester fiber obtained from the copolyester having no high intrinsic viscosity has a problem that the fiber strength is remarkably lowered. On the other hand, in order to solve the problem, it is disclosed that a tetraalkylammonium salt of sulfoisophthalic acid or a tetraalkylphosphonium salt of sulfoisophthalic acid, that is, a compound (B) is copolymerized with a polyester. Since thermal decomposition tends to occur inside, there is a problem that the thermal decomposition reaction tends to proceed when the amount of copolymerization is increased, and it is still difficult to increase the fiber strength. In the copolymer polyester, the metal salt (A) of sulfoisophthalic acid and the compound (B) are used in combination, and the copolymerization amount, copolymerization ratio, glass transition temperature and intrinsic viscosity of the copolymer polyester are determined. It was found that by setting to a specific range, it has both the dyeability with sufficient cationic dye and high fiber strength, and also has physical properties such as good heat setting and easy fixing of crimp. It is. It was surprising that the heat setting property was good and the property of easily fixing crimps was also obtained.

(Glass transition temperature)
It is important that the copolyester has a glass transition temperature (Tg) in the range of 70 to 85 ° C. in a measuring method (temperature increase rate = 20 ° C./min) by DSC (differential scanning calorimetry) method. When the Tg is 70 ° C. or lower, the heat setting property of the polyester fiber obtained by melt spinning is deteriorated, the false twist crimping processability is deteriorated, and the polyester fiber is made of the copolymer polyester. There is a possibility that the texture of the fabric obtained from the above will deteriorate. As a method for lowering the glass transition temperature, adipic acid, sebacic acid, diethylene glycol, polyethylene glycol and the like are copolymerized. In the present invention, these copolymer components satisfy the above glass transition temperature conditions. As long as it is within the range, it may be minutely copolymerized. A preferable value range of Tg is 71 to 80 ° C.

  Usually, since it is known that the glass transition temperature of polyethylene terephthalate is about 70 to 80 ° C., in the present invention, the copolymer polyester may be copolymerized with other copolymer components as described above. However, it is not preferable to copolymerize a component that significantly lowers the glass transition temperature as a result of copolymerization. In order to set the glass transition temperature within the above range, for example, the type and copolymerization ratio of the compounds that may be copolymerized listed in the description of the above-described copolymerized polyester are appropriately adjusted for copolymerization. I can list them.

(Intrinsic viscosity)
It is important that the intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the copolyester is in the range of 0.55 to 1.00 dL / g. When the intrinsic viscosity is 0.55 dL / g or less, the strength of the resulting polyester fiber is insufficient. On the other hand, when the intrinsic viscosity is 1.00 dL / g or more, the melt viscosity becomes too high and melt molding becomes difficult. In addition, the production cost in the polycondensation step of the copolyester is greatly increased by the solid phase polymerization method subsequent to the melt polymerization method, which is not preferable. The intrinsic viscosity of the copolyester is more preferably in the range of 0.60 to 0.90 dL / g. In order to make the intrinsic viscosity of the copolyester in the range of 0.55 to 1.00 dL / g, it is difficult to adjust the final polymerization temperature and polymerization time during melt polymerization, or only by the melt polymerization method. The solid phase polymerization can be appropriately adjusted. In the present invention, the metal salt (A) of sulfoisophthalic acid and the compound (B) are copolymerized with polyethylene terephthalate so as to satisfy the above mathematical formulas (1) and (2). It becomes possible to make an intrinsic viscosity into 0.55-1.00 dL / g.

(DEG content)
The diethylene glycol contained in the copolymerized polyester is preferably 2.5% by weight or less. More preferably, it is 2.2 wt% or less, and still more preferably 1.85 to 2.2 wt%. In general, when producing a cationic dyeable polyester, a small amount of alkali metal salt, alkaline earth metal salt, hydroxide is used as a DEG inhibitor to suppress the amount of diethylene glycol (DEG) by-produced in the polyester production process. At least one kind such as tetraalkylphosphonium, tetraalkylammonium hydroxide, and trialkylamine is used, and in the case of the present invention, the total moles of the metal salt (A) of sulfoisophthalic acid and the compound (B) are used. It is preferable to add about 1 to 20 mol% with respect to the amount.

(About the production method of copolyester)
The production of the copolyester is not particularly limited, and a conventionally known polyester production method is used. That is, a low polymer is produced by a direct esterification reaction between terephthalic acid and ethylene glycol, or by an ester exchange reaction between an ester-forming derivative of terephthalic acid represented by dimethyl terephthalate and ethylene glycol. Next, this reaction product is produced by heating under reduced pressure in the presence of a polycondensation catalyst to carry out a polycondensation reaction until a predetermined polymerization degree is reached. It is possible to use a generally known production method for the method of copolymerizing an aromatic dicarboxylic acid containing sulfoisophthalic acid and / or an ester derivative thereof (metal salt (A) and compound (B) of sulfoisophthalic acid). it can. These compounds can be added to the reaction step at any time from the beginning of the transesterification or esterification reaction to the start of the polycondensation reaction.

  Moreover, the catalyst compound used when performing a normal transesterification reaction can also be used about the catalyst at the time of transesterification. As the polycondensation catalyst, commonly used antimony compounds, germanium compounds, and titanium compounds can be used. Further, a reaction product of a titanium compound and an aromatic polyvalent carboxylic acid or an anhydride thereof, or a reaction product of a titanium compound and a phosphorus compound may be used.

(About other additives)
The copolymer polyester may contain a small amount of additives as necessary, for example, an antioxidant, a fluorescent whitening agent, an antistatic agent, an antibacterial agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a light-shielding agent, or a gloss. It may contain an eraser. In particular, antioxidants and matting agents are particularly preferably added.

(About melt spinning)
There is no restriction | limiting in particular in the spinning method of the said copolyester, A conventionally well-known method is employ | adopted. That is, it is preferable to produce the dried copolyester by melt spinning at a temperature in the range of 270 to 300 ° C., and the spinning speed of the melt spinning is preferably 400 to 5000 m / min. When the spinning speed is in this range, the polyester fiber obtained has sufficient strength and can be wound stably. Furthermore, it is preferable that the undrawn yarn or the partially drawn yarn obtained by the above-described method is drawn in a range of about 1.2 to 6.0 times in the drawing step. This stretching may be performed after winding the unstretched polyester fiber once, or may be performed continuously without winding. The shape of the die used for spinning is not particularly limited, and is round, flat, constricted flat, triangular, quadrangular, etc., three or more multi-leafed, C-shaped, H-shaped, and X-shaped. Any of a hollow cross section may be sufficient.

  The copolymer polyester fiber thus obtained has a fiber strength (tensile strength) of 2.6 cN / dtex or more (preferably 2.8 cN / dtex or more, particularly preferably 3.0 to 5.0 cN / dtex). preferable. The copolymer polyester fiber having such fiber strength can be obtained by spinning and stretching the copolymer polyester as described above.

  Here, an ordinary cationic dyeing agent such as 5-sodium sulfoisophthalic acid is copolymerized with a polyester such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, stereocomplex polylactic acid, or the like. The dyeable polyester is excluded from the present invention because it cannot be dyed at normal pressure.

  In the present invention, the polyester filament yarn A (or sea island type composite fiber filament yarn for polyester filament yarn A) and the normal pressure cationic dyeable filament yarn B are woven and knitted, and if necessary, The fabric is subjected to an alkaline aqueous treatment, and the sea component of the sea-island composite fiber is dissolved and removed with an alkaline aqueous solution, whereby the sea-island composite fiber filament yarn is made into a polyester multifilament yarn A having a single fiber diameter of 10 to 1000 nm. The fabric is dyed with a cationic dye. At that time, it is preferable that the fabric is knitted using only the polyester filament yarn A (or sea-island type composite fiber filament yarn for polyester filament yarn A) and the cationic dyeable filament yarn B, but with respect to the total weight of the fabric. If it is 20% by weight or less, other fibers may be contained. Moreover, it is preferable that the weight ratio with respect to the total weight of the textile fabric of the said polyester filament yarn A exists in the range of 10 to 40 weight%. On the other hand, the weight ratio of the normal pressure cationic dyeable filament yarn B to the total weight of the fabric is preferably in the range of 60 to 90% by weight.

  Moreover, the structure | tissue of a fabric is not specifically limited, A normal woven fabric or a knitted fabric may be sufficient. For example, in the case of a woven fabric, a three-fold structure such as plain weave, oblique weave, satin woven, etc. Examples are velvet. The number of layers is not particularly limited and may be a single layer or a fabric having a multilayer structure of two or more layers.

In particular, it is preferable that the polyester filament yarn A and the cationic dyeable filament yarn B are arranged in the woven fabric as follows.
That is, in a preferred embodiment (1), the fabric is a woven fabric, and the polyester filament yarn A and the normal pressure cationic dyeable filament yarn B are regularly arranged on the warp and / or weft of the woven fabric. . Specifically, they are arranged alternately or alternately (for example, one: plural, plural: one, plural: plural, or a combination thereof).

  In a preferred embodiment (2), the fabric is a woven fabric, and one of warp and weft of the woven fabric contains the polyester filament yarn A, and the other is the normal pressure cationic dyeable filament yarn. B is included. For example, when the polyester filament yarn A is included in the warp and the polyester filament yarn A is included in the weft, the polyester filament yarn A is included in the warp and the polyester filament yarn A is included in the weft. Is done.

  In a preferred embodiment (3), the fabric has a multilayer structure having a multilayer structure of two or more layers, wherein the polyester filament yarn A is contained in at least one layer, and the atmospheric pressure cationic dyeing is contained in another layer. Woven filament yarn B is included. For example, when the fabric has a two-layer structure, the surface layer includes the polyester filament yarn A and the back layer includes the cationic dyeable filament yarn B, and the fabric has a two-layer structure. The case where the cationic dyeable filament yarn B is contained in the surface layer and the polyester filament yarn A is contained in the back layer is exemplified. In particular, the fabric preferably has a multilayer structure of three or more layers, and the outermost layer or the innermost layer contains the polyester filament yarn A, and the other layer contains the cationic dyeable filament yarn B. For example, when the fabric has a three-layer structure, the outermost layer includes the polyester filament yarn A, and the other layer includes the atmospheric pressure cationic dyeable filament yarn B, the fabric has a three-layer structure. Examples include the case where the outermost layer includes the normal pressure cationic dyeable filament yarn B and the other layer includes the polyester filament yarn A.

  In a preferred embodiment (3), the woven fabric includes the polyester filament yarn A and the atmospheric pressure cationic dyeable filament yarn B, and the polyester filament yarn A and / or the cationic dyeable filament yarn B is a composite yarn. Included in the fabric as part. Here, examples of the composite yarn include air-mixed yarn obtained by interlace processing, Taslan (registered trademark) processing, composite false twist crimped yarn, covering yarn, and the like. At that time, it is preferable that the composite yarn has a core-sheath structure in which one of the polyester filament yarn A and the normal pressure cationic dyeable filament yarn B is located in the core portion and the other is located in the sheath portion. .

  Moreover, when dyeing such a fabric with a cationic dye, the cationic dye used may be a normal cationic dye. The dyeing machine may be a normal dyeing machine such as a liquid dyeing machine, a beam dyeing machine, or a jigger, and is not particularly limited.

  In addition, in the process before and / or after the dyeing process, various processes such as conventional scouring, relaxation, pre-setting, and final setting may be performed. In addition, various processing that provides functions such as brushed processing, water repellent processing, calendar processing, ultraviolet shielding or antistatic agent, antibacterial agent, deodorant agent, insect repellent agent, phosphorescent agent, retroreflective agent, negative ion generator, etc. Additional applications may be applied.

In the dyed dyeing fabric thus obtained, the normal pressure cationic dyeable filament yarn B is colored with a cationic dye, thereby having excellent color developability and dyeing fastness.
In addition, the fabric strength is high. Furthermore, since it can dye | stain by a normal pressure, there is little environmental impact.

  Here, when the polyester filament yarn A is made of a cationic dyeable polyester, it is colored with a cationic dye, but when it is made of a cationic non-dyeable polyester, it is not colored with a cationic dye. In addition, since the dyed fabric includes the polyester filament yarn A having a single fiber diameter of 10 to 1000 nm, it exhibits a soft texture peculiar to ultrafine fibers. In that case, it is preferable that the lightness L value is 40 or less. Moreover, it is preferable that the wash dyeing fastness measured by JIS L0844 is 3rd grade or more. Moreover, it is preferable that the fastness to friction dyeing measured by JIS L0849 is 3rd grade or more.

Further, in the dyed fabric, it is preferable that the cover factor of the warp and the cover factor of the weft are both 500 to 5000 (more preferably 500 to 2500). When the cover factor of the warp or weft is less than 500, sufficient color developability may not be obtained, which is not preferable. Conversely, if the cover factor of the warp or weft is greater than 2500, the color developability is improved, but the texture becomes hard, which is not preferable. The cover factor CF in the present invention is represented by the following formula.
Warp cover factor CF _p = (DWp / 1.1) ^1/2 × MWp
Weft cover factor CF _f = (DWf / 1.1) ^1/2 × MWf
[DW _p is the total warp fineness (dtex), MW _p is the warp weave density (main / 2.54 cm), DW _f is the total weft fineness (dtex), and MW _f is the weft weave density (main /2.54 cm) . ]

  Next, the textile product of the present invention is a sportswear, outdoor wear, raincoat, umbrella, men's clothing, women's clothing, work clothes, protective clothing, artificial leather, footwear, heel, It is a textile product selected from the group of curtains, tarpaulins, tents and car seats. Since such a textile product uses the above-mentioned dyed fabric, it has not only a soft texture peculiar to ultrafine fibers, but also excellent color development and dyeing fastness, high fabric strength, and environment. There is little load.

  Next, although the Example and comparative example of this invention are explained in full detail, this invention is not limited by these. In addition, each measurement item in an Example was measured with the following method.

<Dissolution rate> The sea and island polymers are each wound up at a spinning speed of 1000 to 2000 m / min with a 0.3Φ-0.6L × 24H die, and the residual elongation is in the range of 30 to 60%. Then, an 84 dtex / 24 fil multifilament was produced. The weight loss rate was calculated from the dissolution time and the dissolution amount at a bath ratio of 100 at a temperature at which the solvent was dissolved in each solvent.

<Warn Cover Factor CFp and Weft Cover Factor CFf> These are defined by the following equations.
Warp cover factor ^{CFp = (DWp / 1.1) 1/2} × MWp
Weft cover factor CFf = (DWf / 1.1) ^1/2 × MWf
However, DWp is the total warp fineness (dtex), MWp is the warp weave density (main / 2.54 cm), DWf is the total weft fineness (dtex), and MWf is the weft weave density (main / 2.54 cm).

<Dissolution rate> Each of the sea and island polymers is wound up at a spinning speed of 1000 to 2000 m / min with a 0.3Φ-0.6L × 24H die, and the residual elongation is in the range of 30 to 60%. Then, an 84 dtex / 24 fil multifilament was produced. The weight loss rate was calculated from the dissolution time and the dissolution amount at a bath ratio of 100 at a temperature at which the solvent was dissolved in each solvent.

<Texture>
Three testers sensory-evaluate the texture of the fabric surface. Grade 3: Presents a soft and slimy texture peculiar to ultra-fine fibers (nanofibers). Grade 2: Normal. Grade 1: Textures peculiar to ultra-fine fibers. It was evaluated in three stages: not present.

<Single fiber diameter>
After the fabric was photographed with an electron microscope, the single fiber diameter was measured with an n number of 5, and the average value was obtained.

<Lightness L value>
Macbeth COLOR-EYE model M-2020P
L was used to measure the lightness L value represented by the L * a * b * system color display defined in JISZ 8729-1980.

<Washing dyeing fastness>
It was measured according to JIS L0844.

<Friction dyeing fastness>
It was measured according to JIS L0849.

<Tear strength>
It was measured according to JIS L1096-90.

<Environmental impact>
In the dyeing process, when the amount of steam used per batch was 20% or less as compared with normal high-pressure dyeing, it was determined that the environmental load was good.

[Example 1]
Using polyethylene terephthalate as the island component, polyethylene terephthalate copolymerized with 6 mol% of 5-sodium sulfoisophthalic acid and 6% by weight of polyethylene glycol having a number average molecular weight of 4000 as the sea component (dissolution rate ratio (sea / island) = 230), A sea-island type composite unstretched fiber having sea: island = 40: 60 and number of islands = 500 was melt-spun at a spinning temperature of 280 ° C. and a spinning speed of 1500 m / min and wound up once. The obtained undrawn yarn was roller-drawn at a drawing temperature of 80 ° C. and a draw ratio of 2.5 times, and then heat-set at 150 ° C. and wound up. The obtained sea-island type composite drawn yarn (for polyester filament yarn A) was 50 dtex / 10 fil, and the cross section of the fiber was observed with a transmission electron microscope TEM. The shape of the island was round and the diameter of the island was 700 nm. there were.

On the other hand, in a mixture of 100 parts by weight of dimethyl terephthalate, 4.1 parts by weight of dimethyl 5-sodium sulfoisophthalate and 60 parts by weight of ethylene glycol, 0.03 parts by weight of manganese acetate and 0.12 parts by weight of sodium acetate trihydrate. Was added, and the ester exchange reaction was carried out while gradually raising the temperature from 140 ° C. to 240 ° C. while distilling methanol produced as a result of the reaction out of the system. Thereafter, 0.03 part by weight of normal phosphoric acid was added to complete the transesterification reaction.
Thereafter, 0.05 parts by weight of antimony trioxide, 2.8 parts by weight of tetrabutylphosphonate 5-sulfoisophthalate, 0.3 parts by weight of tetraethylammonium hydroxide and 0.003 parts by weight of triethylamine were added to the reaction product. Move to the condensation tank, raise the temperature to 285 ° C., perform the polycondensation reaction at a high vacuum of 30 Pa or less, and perform the reaction when the value of the agitator power in the polycondensation tank reaches a predetermined power or when a predetermined time has elapsed. The chip was finished and chipped according to a conventional method.
The polyester chip thus obtained was dried at 140 ° C. for 5 hours, a raw yarn of 330 dtex / 36 filaments was prepared at a spinning temperature of 285 ° C. and a winding speed of 400 m / min, and then subjected to 4.0 simultaneous drawing and drawing. The yarn was stretched twice to obtain a false twisted yarn (ordinary pressure cationic dyeable filament yarn B) of 83 dtex / 36 filaments.

Next, the whole amount of the normal pressure cationic dyeable filament yarn B is arranged in the warp yarn, two normal pressure cationic dyeable filament yarns B in the weft yarn, and the sea-island type composite drawn yarn (for polyester filament yarn A) 1 Books were arranged alternately, and a plain fabric woven machine was obtained at a weaving density of warp density of 165 pieces / 2.54 cm and weft density of 107 pieces / 2.54 cm. And in order to remove the sea component of the said sea-island type composite stretched yarn, it was reduced by 30% (alkali reduction) at 55 ° C. with a 3.5% NaOH aqueous solution. The woven fabric contained a polyester filament yarn A having a single fiber diameter of 700 nm and an atmospheric pressure cationic dyeable filament yarn B having a single fiber diameter of 15 μm.
Next, a dyeing process was performed using a cationic dye to prepare a woven fabric having a warp density of 182 yarns / 2.54 cm and a weft density of 118 yarns / 2.54 cm. The staining was performed under the following conditions.
CATHILON BLUE CD-FRLH) 0.2 g / L, CD-FBLH 0.2 g / L (both cation dyeable dyes manufactured by Hodogaya Chemical Co., Ltd.), sodium sulfate 3 g / L, acetic acid 0.3 g / L The dyeing was performed at 100 ° C. (normal pressure) for 1 hour at a bath ratio of 1:50.

When the surface of the fabric and the cross section of the warp and the weft were observed with a scanning electron microscope SEM, the sea component was completely dissolved and removed, and the total amount of the warp and the weft of the fabric was super-fine. Confirmed that it was configured. In the obtained woven fabric (dyed fabric), the warp cover factor CFp is 1289, the weft cover factor CFf is 791, the L value is 20, the fastness to washing is 4th grade, and the fastness to friction is 4th grade. It had fastness. The tear strength was as high as 10 cN.
Next, when the T-shirt (sportswear) was obtained and worn using the dyed fabric, it exhibited a soft and slimy texture peculiar to ultra-fine fibers (nanofibers), and had excellent color development and fastness. It was. Moreover, the soft and slimy texture (3rd grade) peculiar to a super extra fine fiber (nanofiber) was exhibited. The evaluation results are shown in Table 1.

[Comparative Example 1]
The same sea-island type composite drawn yarn (for polyester filament yarn A) as in Example 1 is distributed in the warp and weft in a normal amount at a weaving density of warp density of 197 / 2.54 cm and weft density of 121 / 2.54 cm. By this weaving method, a plain fabric woven machine was obtained. And in order to remove the sea component of a sea-island type composite stretched yarn, it was reduced by 30% (alkali reduction) at 55 ° C. with a 3.5% NaOH aqueous solution. The woven fabric contained only the polyester filament yarn A having a single fiber diameter of 700 nm.

Next, dyeing processing was performed using a cationic dye in the same manner as in Example 1 to prepare a woven fabric having a warp density of 217 pieces / 2.54 cm and a weft density of 133 pieces / 2.54 cm.
When the surface of the woven fabric and the cross section of the warp and the weft were observed with a scanning electron microscope SEM, the sea component was completely dissolved and removed, and the total amount of the warp and weft of the woven fabric consisted of ultrafine fibers with excellent uniformity. Confirmed that it has been. In the obtained woven fabric, the warp cover factor CFp is 697, the weft cover factor CFf is 427, the L value is 70, the fastness to washing is the fourth grade, and the fastness to friction is the fourth grade. It was. Moreover, the soft and slimy texture (3rd grade) peculiar to a super extra fine fiber (nanofiber) was exhibited. The tear strength was inadequate at 4 cN. The evaluation results are shown in Table 1.

[Comparative Example 2]
Using a copolymerized polyethylene terephthalate polymer obtained by copolymerizing 2.6 mol% of 5-sodium sulfoisophthalic acid, which is a cationic dye, by a conventional spinning / drawing method, a cationic dyeable polyester multifilament drawn yarn C ( 56 dtex / 24 fil, cationic dyeable filament yarn C) was obtained.
Next, the above-mentioned cationic dyeable polyester multifilament drawn yarn C is arranged in the warp and the weft in the warp and the normal weaving at a weave density of 165 / 2.54 cm and a weft density of 101 / 2.54 cm. A plain fabric woven machine was obtained by the method. The woven fabric contained only a cationic dyeable polyester multifilament drawn yarn C having a single fiber diameter of 15 μm.

Next, a dyeing process was performed using a cationic dye to prepare a woven fabric having a warp density of 182 yarns / 2.54 cm and a weft density of 118 yarns / 2.54 cm. The staining was performed under the following conditions.
(Dyeing bath):
Bismarck Brown B (Trademark, manufactured by Nippon Chemical Co., Ltd.) 3.5% (based on fabric mass)
Irgasol DAM (trademark, manufactured by Ciba Geigy) 1 g / liter acetic acid 0.5 g / liter (dyeing machine):
Liquid dyeing machine (manufactured by Nisaka Seisakusho)
(conditions):
Temperature 130 ° C, time 45 minutes

  When the surface of the woven fabric and the cross section of the warp and the weft were observed with a scanning electron microscope SEM, the sea component was completely dissolved and removed, and the total amount of the warp and weft of the woven fabric consisted of ultrafine fibers with excellent uniformity. Confirmed that it has been. In the obtained woven fabric, the warp cover factor CFp is 1289, the weft cover factor CFf is 791, the L value is 20, the wash fastness is 4th grade, and the friction fastness is 4th grade. The texture became stiff. The tear strength was 8 cN. Moreover, it did not exhibit the texture peculiar to a microfiber (first grade). The evaluation results are shown in Table 1.

[Comparative Example 3]
In the warp yarn, the same cationic dyeable polyester multifilament drawn yarn C as in Comparative Example 2 and two sea-island type composite drawn yarn (for polyester filament yarn A) as in Example 1 are alternately arranged. The same cationic dyeable polyester multifilament drawn yarn C as in Comparative Example 2 and two sea-island type composite drawn yarn (for polyester filament yarn A) as in Example 1 were alternately arranged, and the warp density was 185/2. A plain fabric woven machine was obtained by a normal weaving method at a weaving density of .54 cm and a weft density of 113 / 2.54 cm. And in order to remove the sea component of a sea-island type composite stretched yarn, it was reduced by 30% (alkali reduction) at 55 ° C. with a 3.5% NaOH aqueous solution. The woven fabric contained a polyester filament yarn A having a single fiber diameter of 700 nm and a cationic dyeable polyester multifilament drawn yarn C having a single fiber diameter of 15 μm.

Next, dyeing processing was performed using a cationic dye in the same manner as in Comparative Example 2 to prepare a woven fabric having a warp density of 204 / 2.54 cm and a weft density of 125 / 2.54 cm.
When the surface of the woven fabric and the cross section of the warp and the weft were observed with a scanning electron microscope SEM, the sea component was completely dissolved and removed, and the total amount of the warp and weft of the woven fabric consisted of ultrafine fibers with excellent uniformity. Confirmed that it has been. In the obtained woven fabric, the warp cover factor CFp is 918, the weft cover factor CFf is 562, the L value is 35, the fastness to washing is the fourth grade, and the fastness to friction is the fourth grade. Was. The tear strength was 7 cN. Moreover, the soft and slimy texture (3rd grade) peculiar to a super extra fine fiber (nanofiber) was exhibited. The evaluation results are shown in Table 1.

  According to the present invention, not only the soft texture peculiar to ultra-fine fibers but also excellent color development and dyeing fastness, high fabric strength, low environmental impact, and dyeing the fabric. A dyed fabric and a fiber product using the dyed fabric are provided, and the industrial value thereof is extremely large.

Claims (15)

  A fabric comprising a polyester filament yarn A having a single fiber diameter of 10 to 1000 nm and an atmospheric pressure cationic dyeable filament yarn B having a single fiber diameter of more than 1000 nm.   The fabric according to claim 1, wherein the number of filaments of the polyester filament yarn A is 500 or more.   The fabric according to claim 1 or 2, wherein the polyester filament yarn A is a yarn obtained by dissolving and removing a sea component of a sea-island composite fiber composed of a sea component and an island component. The normal pressure cationic dyeable filament yarn B is composed of a copolymerized polyester fiber, and the copolymerized polyester fiber is used as a copolymer component in a metal salt of sulfoisophthalic acid (A) in the acid component and the following formula (I) The compound (B) represented by the formula (1) and (2) are simultaneously satisfied, and the glass transition temperature of the copolymer polyester is in the range of 70 to 85 ° C., and the copolymer The fabric according to any one of claims 1 to 3, wherein the fabric is a copolyester fiber made of a copolyester having an intrinsic viscosity of 0.55 to 1.00 dL / g.

[In the above formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents a quaternary phosphonium ion or a quaternary ammonium ion. ]
3.0 ≦ A + B ≦ 5.0 (1)
0.2 ≦ B / (A + B) ≦ 0.7 (2)
[In the above formula, A is the copolymerization amount (mol%) of the metal salt of sulfoisophthalic acid (A) based on the total acid component constituting the copolyester, and B is the total acid component constituting the copolyester. This represents the copolymerization amount (mol%) of the compound (B) represented by the above formula (I) as a reference. ]   5. The fabric according to claim 1, wherein the fabric is a woven fabric, and the polyester filament yarn A and the normal pressure cationic dyeable filament yarn B are regularly included in the warp and / or weft of the woven fabric. Fabric.   The fabric is a woven fabric, and one of warp and weft of the woven fabric includes the polyester filament yarn A, and the other includes the atmospheric pressure cationic dyeable filament yarn B. The fabric according to any one of the above.   The fabric is a multilayer structure fabric having a multilayer structure of two or more layers, wherein the polyester filament yarn A is contained in at least one layer, and the atmospheric pressure cationic dyeable filament yarn B is contained in another layer. The fabric in any one of 1-4.   The fabric has a multilayer structure of three or more layers, the polyester filament yarn A is included in the outermost layer or the innermost layer, and the atmospheric pressure cationic dyeable filament yarn B is included in the other layer. Fabric.   The fabric includes the polyester filament yarn A and the normal pressure cationic dyeable filament yarn B, and the polyester filament yarn A and / or the normal pressure cationic dyeable filament yarn B is included in the fabric as a part of the composite yarn. The fabric according to any one of claims 1 to 4.   The fabric according to claim 9, wherein the composite yarn is any one selected from the group consisting of an air mixed yarn, a composite false twist crimped yarn, and a covering yarn.   A dyed fabric obtained by dyeing the fabric according to any one of claims 1 to 10 with a cationic dye.   The dyed fabric according to claim 11, wherein the lightness L value is 40 or less.   The dyed fabric according to claim 11 or 12, wherein the fastness to washing dyeing measured by JIS L0844 is grade 3 or higher.   The dyed fabric according to any one of claims 11 to 13, wherein the fastness to friction dyeing measured by JIS L0849 is 3 or more.   Sportswear, outdoor wear, raincoat, umbrella, men's clothing, women's clothing, work clothing, protective clothing, artificial leather, footwear, heels, curtains, comprising the dyed fabric according to any one of claims 11 to 14 , Any textile product selected from the group of tarpaulins, tents and car seats.