JP2010255128A - Circular knitted fabric and fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a circular knitted fabric and a fiber product each having excellent color fastness. <P>SOLUTION: A yarn made of specific copolyester fibers is used to obtain a circular knitted fabric which is, if necessary, then dyed with a cationic dye. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a circular knitted fabric and a textile product having excellent dyeing fastness.

Conventionally, circular knitted fabrics are used in a wide range of fields such as inner wear, outer wear, and sports wear because they are excellent in stretchability and fit (see, for example, Patent Document 1). In addition, polyethylene terephthalate fiber or the like is widely used as the fiber constituting the circular knitted fabric.
However, a circular knitted fabric made of polyethylene terephthalate fibers is excellent in stretchability but is not sufficient in terms of dyeing fastness.

JP 2006-328567 A

  This invention is made | formed in view of said background, The objective is to provide the circular knitted fabric and textiles which have the outstanding dyeing fastness.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained a circular knitted fabric using a specific copolymer polyester fiber, and then subjected to a dyeing process using a cationic dye. The present inventors have found that a circular knitted fabric having a knitted fabric can be obtained, and have completed the present invention by further intensive studies.

  Thus, according to the present invention, “a circular knitted fabric including a yarn composed of a copolymerized polyester fiber, wherein the copolymerized polyester fiber is a metal salt of sulfoisophthalic acid in the acid component (A) as a copolymerized component. And the compound (B) represented by the following formula (I) is contained so as to satisfy the following formulas (1) and (2) simultaneously, the glass transition temperature of the copolyester is in the range of 70 to 85 ° C., And a circular knitted fabric characterized by being a copolyester fiber comprising a copolyester having an intrinsic viscosity of the copolyester in the range 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 that case, it is preferable that diethylene glycol content in the said copolyester is 2.5 weight% or less. The metal salt (A) of sulfoisophthalic acid is preferably 5-sodium sulfoisophthalic acid or dimethyl 5-sodium sulfoisophthalate. Moreover, it is preferable that the compound (B) represented by the said formula (I) is 5-sulfoisophthalate tetrabutylphosphonium or 5-sulfoisophthalate dimethyltetrabutylphosphonium. The tensile strength of the yarn is preferably 3.0 cN / dtex or more. The single fiber fineness of the yarn is preferably in the range of 0.1 to 2.0 dtex, and the total fineness is preferably in the range of 5 to 50 dtex. The circular knitted fabric is preferably a single-layer circular knitted fabric having a thickness of 0.4 mm or less. The number of needle loops in the knitted fabric is preferably 5000 / (2.54 cm) ² or more.

  However, the number of needle loops of the knitted fabric is a value obtained by multiplying the number of courses per 2.54 cm (course / 2.54 cm) and the number of wales per 2.54 cm (wale / 2.54 cm).

  In the circular knitted fabric of the present invention, it is preferable that a dyeing process is performed at normal pressure using a cationic dye. Moreover, it is preferable that the stretch recovery property of a weft direction is 80% or more. Moreover, it is preferable that anti-snugging property is 3rd grade or more.

  In addition, according to the present invention, there is provided any textile product selected from the group consisting of inner wear, outer wear, and sports wear using the circular knitted fabric.

  According to the present invention, a circular knitted fabric and a textile product having excellent dyeing fastness can be obtained.

It is a figure which shows the knitting structure | tissue of the tengu structure | tissue which can be employ | adopted in the circular knitted fabric of this invention. It is a load-elongation curve drawn when measuring stretch recovery property.

Hereinafter, the present invention will be described in detail.
The copolymerized polyester used in the present invention is a copolymerized 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. A copolyester containing a metal salt of sulfoisophthalic acid (A) as a component and a compound (B) represented by the following formula (I) in a state satisfying the following mathematical formulas (1) and (2) simultaneously: The polyester is characterized in that the glass transition temperature of the copolyester is in the range of 70 to 85 ° C., and the intrinsic viscosity of the copolyester obtained 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 polyester)
The polyester in the present invention 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 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 used in the present invention 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))
In the present invention, the total of the above-mentioned sulfoisophthalic acid metal salt (A) to be copolymerized with the polyester and the above-mentioned compound (B) is based on the total acid component constituting the copolymerized polyester, and the (A) component and (B ) The sum A + B of the components 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 copolymerized polyester of the present invention, the metal salt (A) of sulfoisophthalic acid and the compound (B) are used in combination, the copolymerization amount of both compounds, the copolymerization ratio, the glass transition temperature of the copolymerized polyester and the intrinsic property. By setting the viscosity within a specific range, the dye has sufficient physical properties such as sufficient dyeability with a cationic dye and high fiber strength, good heat setability and easy fixation of crimp. It is surprising that the heat setting property is good and the crimping property is easily fixed.

(Glass transition temperature)
It is important that the copolyester of the present invention has a glass transition temperature (Tg) in the range of 70 to 85 ° C. by a measuring method (temperature increase rate = 20 ° C./min) by DSC (differential scanning calorimetry) method. is there. 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 of the present invention 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 in the present invention 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 in the present invention is not particularly limited, and the metal salt (A) of sulfoisophthalic acid (hereinafter sometimes abbreviated as compound A) and the compound (B) satisfy the condition described in claim 1. Other than this, 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)
In addition, the copolymer polyester in the present invention contains a small amount of additives as necessary, for example, antioxidants, fluorescent whitening agents, antistatic agents, antibacterial agents, ultraviolet absorbers, light stabilizers, heat stabilizers, and light-shielding agents. Or a matting agent etc. may be included. 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 copolyester in this invention, 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 300 to 5000 m / min. When the spinning speed is in this range, the polyester fiber obtained has sufficient strength and can be wound stably. 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.

  In the yarn obtained by melt spinning, the tensile strength of the yarn is preferably 3.0 cN / dtex or more (preferably 3.0 to 5.0 cN / dtex). The yarn having such fiber strength can be obtained by spinning and stretching the copolymer polyester as described above. The single fiber fineness of the yarn is in the range of 0.1 to 2.0 dtex (more preferably 0.1 to 0.9 dtex), and the total fineness is 5 to 50 dtex (more preferably 5 to 40 dtex). Within this range, a thin circular knitted fabric is preferable.

  The yarn is preferably a false twist crimped yarn. As conditions for false twist crimping, the yarn is twisted by a twisting device via a first roller and a heat treatment heater having a set temperature of 90 to 220 ° C. (more preferably 100 to 190 ° C.). In response to this, a method of further introducing a relaxation heat treatment into the second heater region is exemplified. The draw ratio at the time of false twisting is preferably in the range of 0.8 to 1.5, and the false twist number is the number of false twists (T / m) = (32500 / √Dtex) × α. 5-1.5 are preferable, and it is good to set it to 0.8-1.2 rank normally. As the twisting device to be used, a disk-type or belt-type frictional twisting device is suitable because it is easy to thread and there is little yarn breakage, but a pin-type twisting device may also be used. In the false twist crimped yarn, the crimp rate is preferably 3% or more (preferably 10 to 45%) in terms of stretchability.

(About production of circular knitted fabric)
A circular knitted fabric is produced using the copolymerized polyester fiber. At that time, the circular knitted fabric may be composed only of the copolymerized polyester fibers, but other fibers may be included in the circular knitted fabric. Examples of such other fibers include natural fibers such as cotton, hemp and silk, regenerated fibers such as rayon, semi-synthetic fibers such as acetate, polyester fibers represented by polyethylene terephthalate, polytrimethylene terephthalate, polylactic acid, and the like. Examples include synthetic fibers such as ether ester fibers, acrylic fibers, nylon fibers, aramid fibers, and polyurethane fibers. Especially, when the elastic fiber yarn which consists of a polyurethane fiber, a polyetherester fiber, etc. is contained in a circular knitted fabric, the stretch property of a circular knitted fabric further improves and it is preferable.

  In addition, the knitting structure of the circular knitted fabric is not limited, but a tengu or a platen tengu in which a composite loop is formed by two kinds of yarns in the knitting structure of a tengu, and at that time, a type of yarn using an elastic fiber yarn Tengu and the like are preferably exemplified. Of these, a single-layer circular knitted fabric having a thickness of 0.4 mm or less is preferable.

Further, when the number of needle loops of the knitted fabric is 5000 pieces / (2.54 cm) ² or more, it is preferable that the structural displacement hardly occurs when the circular knitted fabric is stretched, and sufficient stretch recovery is obtained. Moreover, the anti-snugging property as described later can be obtained by increasing the density in this way.

  However, the number of needle loops of the knitted fabric is a value obtained by multiplying the number of courses per 2.54 cm (course / 2.54 cm) and the number of wales per 2.54 cm (wale / 2.54 cm).

  As the circular knitting machine to be used, it is preferable to use a high gauge circular knitting machine of 46 gauge or higher (for example, VXAC-3S 46G30 inch manufactured by Fukuhara Seiki Co., Ltd.) because a high-density circular knitted product can be obtained.

(About dyeing process)
The dyeing process is preferably performed using a cationic dye. When dyeing is performed using a cationic dye, the cationic dye is firmly adsorbed to the fiber by ionic bonding, so that excellent dyeing fastness can be obtained. Dyeing with disperse dyes may not provide sufficient dyeing fastness. Such a cationic dye may be a commercially available ordinary cationic dye. The dyeing process may be dyed at high pressure, but the copolymer polyester fiber structure can be dyed at normal pressure (100 ° C.), so it can be dyed at normal pressure (100 ° C.). It is preferable because it is friendly to the global environment and can reduce the dyeing cost. Note that there is no problem using a dyeing assistant or the like at the time of dyeing.

(Other processing)
Such fabric may be subjected to normal alkali weight reduction processing as necessary. In addition, conventional water-absorbing processing, water-repellent processing, brushed processing, UV shielding or various processing that provides functions such as antibacterial agents, deodorants, insect repellents, phosphorescent agents, retroreflective agents, negative ion generators, etc. Additional applications may be applied.

  For example, the water-absorbing process is preferably exemplified by subjecting the knitted fabric to a bath treatment with a hydrophilizing agent such as PEG diacrylate and its derivatives or a polyethylene terephthalate-polyethylene glycol copolymer during dyeing.

  The circular knitted fabric thus obtained has not only stretchability but also excellent dyeing fastness. Moreover, when such a circular knitted fabric has such a high density, it has excellent stretch recovery properties and anti-snugging properties. Here, it is preferable that the stretch recovery property in the width direction tested by the following test method is 80% or more.

  First, two test pieces having a width of 5 cm and a length of 20 cm are collected in the width direction, and a test piece is prepared by accurately marking the center of the test length of 10 cm. Next, using a tensile tester with a self-recording device, an initial load of 196.1 mN (20 gf) is applied and the test piece is held so that the holding interval is 10 cm, and 14.7 N (1.5 kgf) constant at a tensile speed of 30 cm / min. After extending to the load, immediately return to the position at the same speed, and draw a load-extension curve as shown in FIG. Immediately after the test, the test piece is removed from the chuck, and the residual elongation (up to 0.01 cm) is measured with a scale.

The stretch recovery property (%) is obtained from the drawn curve by the following formula, and is expressed by an average value of two times.
Stretch recovery (%) = (OB (cm) −residual elongation (cm)) / OB (cm) × 100
Further, the anti-snugging property is preferably a grade 3 or higher as measured by JIS L 1058-1998 7.4 ICI type pilling tester method.

  Next, the textile product of the present invention is any textile product selected from the group consisting of inner wear, outer wear, and sports wear using the circular knit fabric. Since such a textile product uses the circular knitted fabric, it has not only stretchability but also excellent dyeing fastness.

  Hereinafter, although the present invention is explained using an example, the present invention is not limited to this example. In addition, the physical property in an Example was measured with the following method.

(1) Intrinsic viscosity:
A dilute solution obtained by dissolving a polyester sample in orthochlorophenol at 100 ° C. for 60 minutes was determined from a value measured at 35 ° C. using an Ubbelohde viscometer. The intrinsic viscosity of the tip is referred to as ηC, and the intrinsic viscosity of the undrawn yarn after spinning is referred to as ηF.

(2) Diethylene glycol (DEG) content:
The polyester sample chip was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposition product was measured using gas chromatography (HP 6850, manufactured by Hewlett-Packard Company).

(3) Glass transition temperature (Tg) of polymer:
Using a differential scanning calorimeter (DSC manufactured by Seiko Instruments Inc .: Q10 type), the temperature was increased at a rate of temperature increase of 20 ° C./min.

(4) Tensile strength (breaking strength) and tensile elongation (breaking elongation) of polyester fiber
Measurement was performed by the method described in JIS L1013: 1999 8.5. The tensile strength (breaking strength) is defined as fiber strength.

(5) Mass per unit area The mass per unit area of JIS L 1096 was measured.

(6) Cationic dyeability:
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 3g
/ L, dyed in a dyeing solution of 0.3 g / L of acetic acid at 100 ° C. (normal pressure) for 1 hour at a bath ratio of 1:50, and the dyeing rate was determined by the following formula.
Dyeing rate = (OD ₀ −OD ₁ ) / OD ₀ × 100
OD ₀ : Absorbance at 576 nm of the dye solution before dyeing OD ₁ : Absorbance at 576 nm of the dye solution after dyeing In the examples of the present invention, those having a dyeing rate of 98% or more were judged to have good dyeability.

(7) Dye transfer contamination fastness The test piece (5 cm × 5 cm) and the white cloth identical to the test piece were sandwiched between two aluminum plates so that the examined fabric and the attached piece (5 cm × 5 cm) were in contact with each other. After that, a load of 44.1 N (4.5 kgf) was applied on the aluminum plate, and heat treatment was performed at 120 ° C. for 80 minutes with a constant temperature heat treatment machine, and the state of dye transfer from the test piece to the attached white cloth was determined as a contamination gray. The grade was determined to 1-5 grade on a scale. The higher the grade, the better the fastness.

(8) Thickness The thickness of the knitted fabric was measured according to JIS L 1018-1998 6.5.

(9) Number of needle loops It was calculated by multiplying the number of courses (course / 2.54 cm) per 2.54 cm of the knitted fabric and the number of wales (wale / 2.54 cm).

(10) Preparation of Test Specimens Two test pieces having a width of 5 cm and a length of 20 cm were collected in the transverse direction, and a test piece was prepared by accurately marking the center at a test length of 10 cm.

(11) Stretch recovery property Using a tensile tester with a self-recording device, an initial load of 196.1 mN (20 gf) is applied and the test piece is held so that the holding interval is 10 cm, and 14.7 N (1 at a tensile speed of 30 cm / min). 0.5 kgf) After extending to a constant load, it was immediately returned to its position at the same speed, and a load-elongation curve as shown in FIG. 2 was drawn. Immediately after the test, the test piece was removed from the chuck, and the residual elongation (up to 0.01 cm) was measured with a scale.
Stretch recovery (%) was calculated from the drawn curve by the following formula and expressed as an average of two times.
Stretch recovery (%) = (OB (cm) −residual elongation (cm)) / OB (cm) × 100

(12) Anti-snugging property JIS L 1058-1998 7.4 Anti-snugging property was evaluated by the ICI type pilling tester method.

[Example 1]
Add 0.03 parts by weight of manganese acetate and 0.12 parts by weight of sodium acetate trihydrate to 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. Then, the temperature was gradually raised from 140 ° C. to 240 ° C., and the ester exchange reaction was performed while distilling out the 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 copolyester chip thus obtained was dried at 140 ° C. for 5 hours, spun at a spinning temperature of 285 ° C. and drawn to obtain a drawn yarn of 32 dtex / 72 filaments.

Subsequently, a 46G, 30-inch circular knitting machine (VXAC-3S manufactured by Fukuhara Seiki Co., Ltd.) was used to knit a single-layer circular knitted fabric with a tengu structure using the false twisted yarn, and the resulting knitted fabric 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 In the liquid, dyeing was performed at 100 ° C. (normal pressure) for 1 hour at a bath ratio of 1:50, and a dry heat setting at 170 ° C. was performed as a final set.
In the obtained knitted fabric, the thickness is 0.15 mm, the basis weight is 54 g / m ² , the density is 83 courses / 2.54 cm, 85 wales / 2.54 cm, the number of needle loops is 7055 pieces / (2.54 cm) ² , The stretch recovery property in the transverse direction was 82%, and the stretch recovery property was excellent despite the thin circular knitted fabric. In addition, since the cationic dye is ionically bonded to the fiber, the fastness to dye transfer contamination is 4-5. Details of the production conditions and evaluation results of the copolyester are shown in Table 1. The anti-snugging property was grade 3-4.
Moreover, when sports clothing (T-shirt) was obtained and worn using the knitted fabric, it had excellent dyeing fastness.

[Example 2]
A 46G, 30-inch circular knitting machine (VXAC-3S manufactured by Fukuhara Seiki Co., Ltd.) was used, and the same drawn yarn and polyurethane monofilament (Operontex Co., Ltd., total fineness 11 dtex / 1 fil) were used. Then, a single-layer circular knitted fabric having a bare tengu structure was knitted, and the obtained knitted fabric was dyed in the same manner as in Example 1.
In the obtained knitted fabric, the thickness is 0.31 mm, the basis weight is 175 g / m ² , the density is 99 courses / 2.54 cm, 106 wales / 2.54 cm, the number of needle loops is 10494 pieces / (2.54 cm) ² , The stretch recovery in the width direction was 88%, and the stretch recovery was excellent despite the thin circular knitted fabric. In addition, since the cationic dye is ionically bonded to the fiber, the fastness to dye transfer contamination is 4-5.

[Comparative Example 1]
In Example 1, a polyethylene terephthalate chip was used instead of the copolyester chip. Moreover, it carried out similarly to Example 1 except having carried out the high-pressure dyeing | staining at 130 degreeC using the disperse dye (Nippon Kayaku Co., Ltd. product, Kayalon Polyester Blue2R-SF) in the case of a dyeing process.
The resulting knitted fabric had a dye transfer contamination fastness of 1-2, because the disperse dye was not ionically bonded to the fiber.

  According to the present invention, a circular knitted fabric and a textile product having excellent dyeing fastness are provided, and their industrial value is extremely large.

Claims (12)

A circular knitted fabric including yarns made of copolymerized polyester fibers,
The copolymerized polyester fiber has, as a copolymerization component, a metal salt (A) of sulfoisophthalic acid and a compound (B) represented by the following formula (I) in the acid component, the following formulas (1) and (2): A copolyester containing the copolyester having a glass transition temperature in the range of 70 to 85 ° C. and an intrinsic viscosity of the copolyester in the range of 0.55 to 1.00 dL / g. A circular knitted fabric characterized by being a copolyester fiber comprising:

[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. ]   The circular knitted fabric according to claim 1, wherein the content of diethylene glycol in the copolymerized polyester is 2.5% by weight or less.   The circular knitted fabric according to claim 1 or 2, wherein the metal salt (A) of sulfoisophthalic acid is 5-sodium sulfoisophthalic acid or dimethyl 5-sodium sulfoisophthalate.   The circular knitted fabric according to any one of claims 1 to 3, wherein the compound (B) represented by the formula (I) is tetrabutylphosphonium 5-sulfoisophthalate or dimethyltetrabutylphosphonium 5-sulfoisophthalate. .   The circular knitted fabric according to any one of claims 1 to 4, wherein a tensile strength of the yarn is 3.0 cN / dtex or more.   The circular knitted fabric according to any one of claims 1 to 5, wherein the single fiber fineness of the yarn is in the range of 0.1 to 2.0 dtex, and the total fineness is in the range of 5 to 50 dtex.   The circular knitted fabric according to any one of claims 1 to 6, wherein the circular knitted fabric is a single-layer circular knitted fabric having a thickness of 0.4 mm or less. The circular knitted fabric according to any one of claims 1 to 7, wherein the number of needle loops of the knitted fabric is 5000 pieces / (2.54 cm) ² or more.
However, the number of needle loops of the knitted fabric is a value obtained by multiplying the number of courses per 2.54 cm (course / 2.54 cm) and the number of wales per 2.54 cm (wale / 2.54 cm).   The circular knitted fabric according to any one of claims 1 to 8, wherein the circular knitted fabric is dyed at atmospheric pressure using a cationic dye.   The circular knitted fabric according to any one of claims 1 to 9, wherein stretch recovery in the transverse direction is 80% or more.   The circular knitted fabric according to any one of claims 1 to 10, wherein the anti-snugging property is grade 3 or higher.   A textile product selected from the group consisting of innerwear, outerwear, and sportswear, wherein the circular knitted fabric according to any one of claims 1 to 11 is used.

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