JPH0598566A - Polyester cloth - Google Patents

Abstract

(57) [Summary] [Purpose] It has an excellent silk-like texture and at the same time can express high-level dyeing effects such as different color dyeing effect and marbling effect, and is excellent in mechanical properties such as strength and abrasion resistance. Obtain a fabric. [Constitution] 0.5 to phosphonium sulfonate base conversion
A fabric is composed of a polyethylene terephthalate-based polyester fiber (A) copolymerized with an amount of 2.0 mol% of a compound represented by the following formula and a polyester fiber (B) substantially consisting of polyethylene terephthalate, and then an alkali Apply weight reduction processing.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is capable of expressing a high-quality dyeing effect such as a different color dyeing effect and a marbling effect while having a good silk-like texture, and mechanical properties such as strength and abrasion resistance. Excellent polyester fabric

[0002]

BACKGROUND OF THE INVENTION Polyester is widely used as a fiber because it has many excellent properties, but it has low dyeability and is difficult to dye, especially with a dye other than a disperse dye. Various proposals have been made to improve this dyeability,
As one of them, a method is known in which an isophthalic acid component containing a metal sulfonate group such as 5-Na sulfoisophthalic acid is copolymerized in the polyester main chain, preferably in an amount of 2 to 5 mol%, so that it can be dyed with a cationic dye. (See Japanese Examined Patent Publication No. 34-10497) and is widely used industrially.

On the other hand, in order to give silk-like soft and good feel to a woven or knitted product made of polyester fiber, a method of alkali reduction treatment is known, and in this case, it is about 20% by weight to 30% by weight. Weight loss is done.

According to this alkali weight loss treatment method,
When a regular polyester fiber and the above-mentioned cationic dye-dyeable polyester fiber are woven or knitted for the purpose of achieving a good texture and a different color dyeing effect or a marbling effect, an alkali weight reduction process of about 20% by weight or more is performed. However, there is a defect that the cationic dye-dyeable polyester fiber is almost decomposed.

That is, when the above cationic polyester dyeable copolyester fiber is subjected to the alkali reduction treatment which is usually carried out in order to improve the texture of the woven or knitted fabric, the dissolution rate of the fiber by alkali is extremely high, Not only is it difficult to perform a stable weight loss treatment under the conditions that are usually adopted industrially (for example, 3% sodium hydroxide solution at 100 ° C), but the strength of the alkali-treated yarn is remarkably reduced. It was difficult to apply processing.

Various proposals have heretofore been made in order to solve the drawbacks of the cationic dye-dyeable polyester fiber. As one of them, the present inventors have previously used a sulfonate compound having one ester-forming functional group such as an m-metal sulfobenzoic acid compound as a cationic dye-dyeing agent, and used the sulfonate compound of polyester. By copolymerizing at the end of the molecular chain, the polyester fiber finally obtained exhibits cationic dye dyeability, the rate of alkali weight reduction is markedly reduced, and the decrease in yarn strength due to alkali weight reduction is also significantly reduced. It was discovered and proposed (see Japanese Patent Publication No. 2-19228). However, such a polyester fiber has poor dyeability and sharpness as compared with a polyester fiber obtained by copolymerizing 5-Nasulfoisophthalic acid, though the dye is completely adsorbed when dyed with a cationic dye. It was damaged and had a dull hue, and it was difficult to obtain a deep color.

Further, a woven fabric obtained by weaving a different shrinkage mixed yarn composed of polyester fiber dyeable with a cationic dye, which is obtained by adding sulfoisophthalate to 0.8 mol% or more and 1.8 mol% or less of polyethylene terephthalate, and a weight loss ratio of 5 Of a fabric having a silky feel, which has been alkali-reduced in the range of 30% to 30% and is dyed with a cationic dye (JP-A-59).
-53774) and sulfoisophthalic acid.
8 mol% or more and 1.8 mol% or less Polyethylene terephthalate Weaving a woven fabric made of strongly twisted yarn made of polyester fiber dyeable with a cationic dye added to polyethylene terephthalate.
A method for obtaining a woven fabric having a silky texture by subjecting it to alkali reduction treatment in the range of 30% or more and then dyeing it with a cationic dye at a temperature of 120 ° C. or higher (Japanese Patent Publication No. 314951) is proposed. .. However, the effect of improving the alkali resistance is insufficient by the technique of simply reducing the amount of the widely used sulfoisophthalic acid-based cationic dye dyeing agent, and the interwoven and interwoven with the regular polyester fiber is insufficient. Not only can it withstand the high alkali reduction processing of knitted fabrics, but the dyeing up when dyed with a cationic dye is greatly deteriorated, vividness is lost, and a dull hue is obtained, and deep colors are obtained. Since it does not exist, it has a serious drawback that high-quality color expression cannot be performed.

Further, the isophthalic acid component containing a metal sulfonate group is 0.7 to 2.4 mol% and the molecular weight is 90 to 90%.
Modified polyester fiber copolymerized with 0.2 to 10% by weight of 6,000 glycol components and having a degree of polymerization of 80 to 100 (see JP-A-57-210014).
Or 0.1 to 4% by weight of inert inorganic fine particles having an average primary particle diameter of 100 mμ or less, and an isophthalic acid component containing a metal sulfonate group of 0.7 to 2.4 mol% and a molecular weight of 90 to 0.2 to 6,000 glycol components
10% by weight is copolymerized and the degree of polymerization is 80-100.
A modified polyester fiber (Japanese Patent Application Laid-Open No. 58-149326) in which fine vertical dents are provided on the fiber surface by alkali dissolution treatment is proposed. In these fibers, the decrease in the cationic dye dyeability due to the decrease in the amount of the cationic dye dyeing agent is compensated by copolymerizing a specific amount of a glycol component having a molecular weight of 90 to 6,000. However, the decrease in cation dyeability is certainly small. However, the polyester fiber obtained by copolymerizing the isophthalic acid component having such a metal sulfonate group has a molecular weight of 90 to 6,
Polyethylene glycol (molecular weight 400-6, 6, which is specifically used as a glycol component of 000).
000), polypropylene glycol (molecular weight 2,000)
0), polytetramethylene glycol (molecular weight of 100
0) and EO / THF alternating copolymer (molecular weight of 100
0) and the like all have the effect of significantly increasing the alkali weight loss rate of the finally obtained cationic dye-dyeable polyester fiber, so that if sufficient cation dyeability is attempted, the alkali resistance is unavoidably poor. Turned into
It is not possible to have both excellent cationic dyeability and good alkali resistance. Moreover, the use of such glycol components leads to a significant reduction in lightfastness to light dyeing.

Furthermore, according to the present inventor, 5-tetra-n
A modified polyester fiber obtained by copolymerizing a cationic dye dyeing agent having a phosphonium sulfonate group such as butylphosphonium sulfoisophthalic acid has been proposed (JP-A-1-162822). According to the above, since the thickening action in the molten state, which is inherent in the cationic dye dyeing agent having a conventionally known metal sulfonate group, does not occur, a polymer having a low viscosity and a high degree of polymerization can be easily obtained, By spinning, high-strength cationic dye-dyeable polyester fibers can be easily obtained. However, in the case of the polyester fiber copolymerized with the phosphonium sulfonate-based cationic dyeing agent actually used in the examples of the above-mentioned publications, the corresponding sulfonate metal is obtained by replacing the phosphonium salt with a metal salt. As compared with polyester fiber copolymerized with a salt-type cationic dyeing agent, the rate of alkali weight loss is high and the alkali resistance is poor, so that the object of the present invention cannot be achieved.

As described above, it has all of good mechanical properties such as good cation dyeability sufficiently excellent in sharpness and bathochromatism, excellent alkali resistance, and high strength and high abrasion durability. Conventionally, there has been no cationic dyeable polyester fiber.

[0011]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention, as described above, has good cation dyeability which is sufficiently excellent in sharpness and bathochromic property, excellent alkali resistance, and high strength and high abrasion durability. The present invention provides an alkali-resistant and high-strength cationic dye-dyeable polyester fiber having all of the excellent mechanical properties such as the above, and the thus obtained cationic dye-dyeable polyester fiber is woven or knitted with regular polyester fibers. By applying an alkali weight loss treatment after knitting, it is possible to express a high-quality dyeing effect such as a different color dyeing effect and a marbling effect while exhibiting a silky good texture when dyed with a cationic dye and a disperse dye. Moreover, it is an object of the present invention to provide a polyester cloth capable of giving a cloth excellent in mechanical properties such as strength and abrasion resistance. Such a fabric is capable of expressing a high degree of various colors and textures at the same time and has sufficiently excellent mechanical properties, and thus is particularly useful in the fields of women's clothing and sports clothing in which fashionability is important.

[0012]

In order to achieve the above object, the present inventor has focused on the chemical structure of a cationic dye dyeing agent and has made many studies to synthesize a large number of compounds. As a result, 2,6-naphthalenedicarboxylic acid sulfone has been obtained. Fibers made of polyethylene terephthalate copolymerized with acid phosphonium salt exhibit excellent cationic dye dyeability and excellent color development with vividness and depth, and also have high strength, and also have a specific alkali weight loss rate. It has been found that the decrease in yarn strength due to the alkali weight reduction is extremely small, and the increase in the alkali weight reduction rate when another dicarboxylic acid component or diol component is copolymerized is also extremely small. The present invention has been completed as a result of further studies based on such findings.

That is, the present invention is a polyester having an ethylene terephthalate unit as a main repeating unit,
The following general formula (I) is used in an amount of 0.5 to 2.0 mol% in terms of phosphonium sulfonate base, based on the dicarboxylic acid component (excluding organic phosphonium phosphonium salt) constituting the polyester.

[0014]

[Chemical 2]

(In the formula, R ¹ and R ² are each independently a hydrogen atom, — (CH ₂ ) _n H (n = 1 to 6))
Or _{- (CH 2) n OH (} n = 1~6 integer), R _1,
R ₂ , R ₃ and R ₄ are the same or different groups selected from an alkyl group and an aryl group, and m is 1 or 2. ) A polyester fiber (A) made of a polyester obtained by copolymerizing a phosphonium salt of an organic sulfonic acid represented by the formula (1) and a polyester fiber (B) made substantially of polyethylene terephthalate, and being alkali-reduced. It is a polyester cloth.

In the present invention, the polyester having the ethylene terephthalate unit as the main repeating unit constituting the polyester fiber (A) is a polyester having terephthalic acid as the main dicarboxylic acid component and ethylene glycol as the main glycol component. In addition, a small amount, usually 15 mol% or less, of the third component may be copolymerized. The third component which can be copolymerized is isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,18-octadecanedicarboxylic acid. Acids, dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid; oxycarboxylic acids such as P-oxybenzoic acid and glycolic acid, or trimethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, dodecamethylene glycol, neo Dihydroxy compounds such as pentyl glycol, diethylene glycol, and bishydroxyethoxy bisphenol A are exemplified. Among them, copolymerizing an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid is effective in improving dyeability and improving color vividness. Is particularly preferable because it is particularly large depending on the application.

Further, polycarboxylic acids such as trimellitic acid and pyromellitic acid, and polyols such as glycerin, trimethylolpropane and pentaerythritol may be copolymerized within the range where the polyester is substantially linear.

The polyester may be synthesized by any method. For example, when polyethylene terephthalate is explained, usually, terephthalic acid and ethylene glycol are directly esterified, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are used. The first step reaction of reacting with oxide to form a glycol ester of terephthalic acid and / or its low polymer, and heating the reaction product of the first step under reduced pressure until a desired degree of polymerization is reached. It is produced by a second stage reaction in which a polycondensation reaction is carried out.

In the polyester constituting the polyester fiber (A) in the present invention, it is necessary that the above-mentioned polyester is copolymerized with an organic phosphonic acid phosphonium salt represented by the following general formula (I).

[0020]

[Chemical 3]

In the above formula (I), R ¹ and R ² are each independently a hydrogen atom, — (CH ₂ ) _n H (n = 1 to 6).
Is an integer) or — (CH ₂ ) _n OH (n is an integer of 1 to 6), R ₁ , R ₂ , R ₃ and R ₄ are the same or different groups selected from the group consisting of alkyl groups and aryl groups. Show. m is 1 or 2.

Such an organic sulfonic acid phosphonium salt is
Generally, it can be easily synthesized by a reaction between a corresponding organic sulfonic acid and a phosphine, or a reaction between a corresponding organic sulfonic acid metal salt and a phosphonium halide.

Preferred specific examples of the organic sulfonic acid phosphonium salt include 2,6-dicarboxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt, and
6-Dicarboxynaphthalene-4-sulfonic acid ethyltributylphosphonium salt, 2,6-dicarboxynaphthalene-4-sulfonic acid benzyltributylphosphonium salt, 2,6-dicarboxynaphthalene-4-sulfonic acid phenyltributylphosphonium salt, 2 , 6-Dicarboxynaphthalene-4-sulfonic acid tetraphenylphosphonium salt, 2,6-dicarboxynaphthalene-4-sulfonic acid butyltriphenylphosphonium salt, 2,6-dicarboxynaphthalene-4-sulfonic acid benzyltriphenylphosphonium Salt, 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt,
2,6-Dicarbomethoxynaphthalene-4-sulfonic acid ethyl tributylphosphonium salt, 2,6-dicarbomethoxynaphthalene-4-sulfonic acid benzyltributylphosphonium salt, 2,6-dicarbomethoxynaphthalene-4-phenyl phenyl ester Tributylphosphonium salt,
2,6-Dicarbomethoxynaphthalene-4-sulfonic acid tetraphenylphosphonium salt, 2,6-dicarbomethoxynaphthalene-4-sulfonic acid ethyltriphenylphosphonium salt, 2,6-dicarbomethoxynaphthalene-
4-sulfonic acid butyltriphenimephosphonium salt,
2,6-Dicarbomethoxynaphthalene-4-sulfonic acid benzyltriphenylphosphonium salt, 2,6-dicarboxynaphthalene-1-sulfonic acid tetrabutylphosphonium salt, 2,6-dicarboxynaphthalene-1-sulfonic acid tetraphenyl Phosphonium salt, 2,6-dicarbomethoxynaphthalene-1-sulfonic acid tetraphenylphosphonium salt, 2,6-dicarboxynaphthalene-3
-Sulfonic acid tetrabutylphosphonium salt, 2,6-dicarboxynaphthalene-3-sulfonic acid tetraphenylphosphonium salt, 2,6-dicarbomethoxynaphthalene-3-sulfonic acid tetrabutylphosphonium salt, 2,6
-Dicarbomethoxynaphthalene-3-sulfonic acid tetraphenylphosphonium salt, 2,6-dicarboxynaphthalene-4,8-disulfonic acid tetrabutylphosphonium salt, 2,6-dicarboxynaphthalene-4,8-disulfonic acid tetraphenyl Phosphonium salt, 2,6-dicarbomethoxynaphthalene-4,8-disulfonic acid tetrabutylphosphonium salt, 2,6-dicarboxynaphthalene-4,8-disulfonic acid tetrabutylphosphonium salt,
2,6-dicarboxynaphthalene-3,8-disulfonic acid tetraphenylphosphonium salt, 2,6-dicarbomethoxynaphthalene-3,8-disulfonic acid tetrabutylphosphonium salt, 2,6-dicarbomethoxynaphthalene-3 8-disulfonic acid tetrabutylphosphonium salt,
2,6-Dicarbomethoxynaphthalene-3,8-disulfonic acid tetraphenylphosphonium salt, 2,6-dicarbomethoxynaphthalene-3,8-disulfonic acid tetrabutylphosphonium salt, 2,6-dicarbomethoxynaphthalene-3 , 8-Disulfonic acid tetraphenylphosphonium salt, 2,6-dicarbomethoxynaphthalene-3,7-
Disulfonic acid tetrabutylphosphonium salt, 2,6-dicarboxynaphthalene-3,7-disulfonic acid tetraphenylphosphonium salt, 2,6-dicarbomethoxynaphthalene-3,7-disulfonic acid tetrabutylphosphonium salt, 2,6- Dicarbomethoxynaphthalene-3,7-
Disulfonic acid tetraphenylphosphonium salt, 2,6-
Di (β-hydroxyethoxycarbonyl) naphthalene
4-sulfonic acid tetrabutylphosphonium salt, 2,6-
Di (β-hydroxyethoxycarbonyl) naphthalene
4-sulfonic acid tetraphenylphosphonium salt, 2,6
-Di (β-hydroxyethoxycarbonyl) naphthalene-4,8-disulfonic acid tetrabutylphosphonium salt,
2,6-di (β-hydroxyethoxycarbonyl) naphthalene-4,8-disulfonic acid tetraphenylphosphonium salt and the like can be mentioned.

The above-mentioned organic phosphonic acid phosphonium salts may be used alone or in combination of two or more.

The copolymerization of such an organic sulfonic acid phosphonium salt into a polyester can be carried out at any stage before the completion of the above-mentioned polyester synthesis, preferably at any stage before the beginning of the second stage reaction. It may be added. The proportion of the phosphonium salt of an organic sulfonic acid to be copolymerized with the polyester is 0.5 mol% to a phosphonium sulfonate group based on the dicarboxylic acid component (excluding the phosphonium salt of an organic sulfonic acid) constituting the polyester.
It is in the range of 2.0 mol%, preferably in the range of 0.8 to 1.8 mol%. If this copolymerization ratio is less than 0.5 mol%, the polyester fabric finally obtained will have insufficient dyeability with cationic dyes, making it difficult to obtain vivid colors and deep colors, while 2.0 mol% When the amount is larger, the alkali weight loss rate of the organic sulfonic acid phosphonium salt copolyester fiber is remarkably increased, the physical properties of the fabric such as tear strength are deteriorated, and a silky good feeling is obtained. It will be difficult.

When such a phosphonium salt of an organic sulfonic acid is used, the heat resistance of the polymer may be deteriorated, but this problem should be avoided by adding a quaternary onium salt disclosed in JP-A-1-162822. You can

It is not necessary to employ a particular method for forming the cationic dye-dyeable copolyester obtained as described above into a fiber, and a usual polyester fiber melt-spinning method is arbitrarily adopted. For example, 500 to 2,50
A method of spinning, stretching and heat treating at a speed of 0 m / min, 1,
Any method such as a method of spinning at a speed of 500 to 5,000 m / min and simultaneously or sequentially performing drawing and false twisting, a method of spinning at a high speed of 5,000 m / min or more and omitting the drawing step depending on the application Spinning conditions are adopted. The fibers thus obtained may be solid fibers having no hollow portion or hollow fibers having a hollow portion. Further, the outer shape of the cross section of the fiber and the shape of the hollow portion may be circular or irregular.

The intrinsic viscosity of the copolymerized polyester constituting the cationic dye-dyeable polyester fiber is preferably 0.5 or more, more preferably 0.6 or more, and particularly preferably 0.63 or more. silk factor (fiber strength × (elongation) ^1/2) is preferably 25 or more, more preferably 28 or more.

The other polyester fiber (B) which constitutes the fabric of the present invention is required to substantially consist of polyethylene terephthalate, whereby the mechanical properties such as strength and abrasion resistance are finally obtained. A polyester cloth that is excellent and has excellent dyeing fastness can be industrially stably obtained.

The mixing ratio of the polyester fiber (A) made of the above-mentioned copolyester and the polyester (B) is preferably in the range of A: B = 1: 9 to 9: 1.

The mixing method is preferably mixed spinning or mixed twisting for short fibers, mixed fiber or mixed yarn for long fibers, and mixed woven or mixed knitting for woven or knitted products. Further, long fibers and short fibers may be mixed and used.

The mixing may be uniform on the entire surface or may be partially mixed. For example, either component may be used only in the pattern portion of the pattern thread, the pattern weave, or the pattern knitting.

The polyester cloth of the present invention needs to be subjected to an alkali weight reduction treatment, and by performing such an alkali weight reduction treatment, it is possible to obtain a good silky texture.

The alkali weight-reducing treatment is carried out by using an alkaline compound such as sodium hydroxide or potassium hydroxide as an aqueous solution and applying it by a pad method, a spray method, a dipping method or the like, followed by heating, or by applying it to the atmosphere. A known method such as a hanging method is adopted. Usually, the alkali concentration is preferably in the range of 1 to 300 g / l, and the treatment temperature is preferably in the range of normal temperature to 100 ° C. A carrier or the like may be added as an alkali treatment accelerator. It is practical that the weight loss due to alkali is about 5 to 40%.

The polyester fiber (A) and the polyester fiber (B) constituting the polyester cloth of the present invention may optionally contain additives such as a catalyst and a color preventive agent.
A heat-resistant agent, a flame retardant, a fluorescent brightening agent, a matting agent, a coloring agent and the like may be contained.

[0036]

The present invention has the following effects. (1) The cationic dye-dyeable polyester fiber used in the present invention has a large yarn strength before alkali treatment and has a markedly improved alkali resistance. A fabric having the same high strength as regular polyester fabric can be obtained. (2) Since the alkali weight loss rate of the cationic dye-dyeable polyester fiber used in the present invention is close to the alkali weight loss rate of regular polyester fiber, it is easy to obtain a silky good texture by the usual alkali weight loss treatment. it can. (3) Regular polyester fibers are dyed with disperse dyes, and cationic dye-dyeable polyester fibers are dyed clearly with cationic dyes. By using them together, two-color dyeing in one bath becomes possible, and high-quality dyeing products can be obtained. Can be obtained (dyeing effect of different colors, marbling effect, etc.). (4) The fabric of the present invention is resistant to high temperatures, for example, 130 ° C.
Even in dyeing, the deterioration of strength does not pose a problem and the texture can be easily obtained. (5) As described above, the fabric of the present invention enables expression of high-level and various colors and textures at the same time, and has sufficiently excellent mechanical properties and dyeing fastness, so that women who attach importance to fashionability It is especially useful in the field of clothing and sports clothing.

[0037]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples. Parts and% in the examples mean parts by weight and% by weight. The alkali dissolution rate constant k in the examples
(Cm / sec), visual infection color of the dyed cloth, and yarn strength reduction rate were measured by the following methods.

(1) Alkali dissolution rate constant k The alkali dissolution rate constant in the present invention is defined by the following formula.

[0039]

[Equation 1]

The alkali dissolution rate constant in the present invention is
Obtained as follows. The polymer was dried by a conventional method, and a spinneret having 24 circular spinning holes with a diameter of 0.3 mm was used at a spinning speed of 1,100 m / min at 285 ° C.
And then the final drawn yarn has an elongation of 30.
At a draw ratio of 1,200 m / min and a heat treatment of 84 ° C. and a plate heater of 180 ° C. for a heat treatment of 75 denier / 24
Obtain a drawn yarn of filaments. The drawn yarn thus obtained is knitted into a knitted fabric, scoured and preset (180 ° C
(× 45 seconds) and then treated with a 1.0% aqueous sodium hydroxide solution at a boiling temperature for 4 hours to obtain a weight loss rate (dissolved weight fraction). Using the value of the dissolution weight fraction, the alkali dissolution rate constant k is calculated from the above formula.

(2) Visual infection color of dyed cloth The L ^* value, a ^* value, and b ^* value of the dyed cloth were measured using Minolta color difference system CR-200 (Minolta Camera Sales Co., Ltd.) The clear color-forming property was determined by (a ^{* 2} + b ^{* 2} ) ^1/2 . The larger this value is, the larger the vivid color is.

(3) Yarn Strength Reduction Rate The strength of the multifilament obtained by unraveling the cloth before the alkali reduction treatment and the strength of the multifilament obtained by unraveling the cloth after the cation dyeing treatment after the alkali treatment are compared. I asked.

[0043]

Examples 1 to 5 and Comparative Example 1 100 parts of dimethyl terephthalate, 66 parts of ethylene glycol, and 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt (dimethyl terephthalate) in the amounts shown in Table 1. With respect to 0.8 to 2.2 mol%), manganese acetate tetrahydrate 0.03 parts (0.024 mol% relative to dimethyl terephthalate), cobalt acetate as a color matching agent. Tetrahydrate 0.009 parts (0.007 mol% based on dimethyl terephthalate) and 0.19 parts 20% aqueous solution of tetraethylammonium hydroxide as a thermal decomposition inhibitor (0.050 mol% based on dimethyl terephthalate) ) Was placed in a transesterification can, and the temperature was raised from 140 ° C to 230 ° C in a nitrogen gas atmosphere for 4 hours to distill the generated methanol out of the system. Reluctant ester was allowed to exchange reaction. Subsequently, 0.03 part of a 56% aqueous solution of orthophosphoric acid (0.033 mol% with respect to dimethyl terephthalate) was added to the obtained product, and at the same time, the temperature rising / expulsion of excess ethylene glycol was started. After 10 minutes, 0.04 part (0.027 mol%) of antimony trioxide was added as a polycondensation catalyst. When the internal temperature reached 240 ° C., the expulsion of ethylene glycol was terminated, and the reaction product was transferred to the polymerization vessel. Next, decompress from 760 mmHg to 1 mmHg over 1 hour, and at the same time for 3 hours 1 hour.
The internal temperature was increased from 240 ° C to 280 ° C over 0 minutes.
Polymerization was continued for 2 hours at a collecting temperature of 280 ° C. under a reduced pressure of 1 mmHg or less. After the reaction was completed, the polymer was made into chips according to a conventional method. The intrinsic viscosity of the obtained polymer is shown in Table 2.

The obtained polymer was dried by a conventional method and was spun at 285 ° C. at a spinning speed of 1,100 m / min using a spinneret having 24 circular spinning holes having a hole diameter of 0.3 mm. At a draw ratio of 1,200 m / min at a draw ratio such that the obtained drawn yarn has an elongation of 30%, and a temperature of 84 ° C.
Stretching heat treatment was performed using the heating roller of No. 1 and a plate heater of 180 ° C. to obtain a stretched yarn of 75 denier / 24 filament having the strength and the alkali dissolution rate constant shown in Table 2.

On the other hand, polyethylene terephthalate having an intrinsic viscosity of 0.640 was similarly melt-spun and drawn and heat treated,
A 75 denier / 24 filament drawn yarn having a strength of 5.2 g / d, an elongation of 30% and an alkali dissolution rate constant of 3.5 × 10 ⁻⁹ cm / sec was obtained.

Each of these drawn yarns was alternately knitted at intervals of 2 cm to obtain a knitted fabric of 10 cm in total. After scouring and presetting this knitted fabric by a conventional method (180 ° C x 45 seconds),
It was treated with a 1.0% aqueous sodium hydroxide solution at a boiling temperature for 4 hours. The knitted fabric after the alkali treatment was decomposed and the weight loss rate of each was determined. The weight loss rate of the copolyester fiber is as shown in Table 2, and the weight loss rate of the polyethylene terephthalate fiber was 11.2%. ..

Similarly, after knitting the alternate knitted fabric, the knitted fabric subjected to scouring, presetting and alkali reduction is made into Cathilon.
Blue CD-FRLH / Cathillon Blu
eCD-FBLH = 1/1 (Hodogaya Chemical Co., Ltd.) 2%
After dyeing with owf in a dye bath containing 3 g / L of Glauber's salt and 0.3 g / L of acetic acid at 130 ° C. for 60 minutes, soaping was carried out according to a conventional method to obtain a knitted fabric in which only the copolyester fiber portion was dyed blue. .. Using this knitted fabric, the yarn strength reduction rate of each part and the saturation of the dyed part were measured. The yarn strength reduction rate of the polyethylene terephthalate fiber was 12%, and the yarn strength reduction rate of the copolyester fiber and the saturation of the dyed cloth were as shown in Table 2.

[0048]

Example 6 2,6-dicarbomethoxynaphthalene-4,8-disulfonic acid tetrabutylphosphonium salt was used in place of the 2,6-dicarboxylic methoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt used in Example 3. 0.75 mol% based on dimethyl terephthalate
The same procedure as in Example 3 was performed, except that the amount used was (1.5 mol% in terms of phosphonium sulfonate base). The results are shown in Table 2.

[0049]

Example 7 In place of the 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt used in Example 3, 2,6-dicarboxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt was replaced with terephthalic acid. Example 3 was repeated except that the amount used was 1.5 mol% with respect to dimethyl, and the addition timing was after completion of the transesterification reaction. The results are shown in Table 2.

[0050]

Example 8 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetraphenylphosphonium salt was used in place of the 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt used in Example 3. The same procedure as in Example 3 was carried out except that The results were as shown in Table 2.

[0051]

[Example 9] 2,6-di (β-hydroxyethoxycarbonyl) naphthalene-4-sulfonic acid tetrahydrate was used in place of the 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt used in Example 7. Example 7 was repeated except that the butylphosphonium salt was used. The results are shown in Table 2.

[0052]

[Examples 10 and 11] 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt used as a copolymerization component in Example 2 (1.0 mol% copolymerization based on dimethyl terephthalate) In addition to)), azelaic acid was copolymerized as a further copolymerization component in amounts of 2.0 mol% and 10 mol% with respect to terephthalic acid, respectively. The results are shown in Table 2.

[0053]

Comparative Example 2 Instead of the 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt used in Example 3, methyl m-sodium sulfobenzoate was added in an amount of 1.5 mol% based on dimethyl terephthalate. Except that 0.112 parts of sodium acetate trihydrate (0.16 mol% relative to dimethyl terephthalate) is used as an ether formation inhibitor instead of tetraethylammonium hydroxide which is a thermal decomposition inhibitor. The same procedure as in Example 3 was performed. The results are shown in Table 2.

[0054]

Comparative Example 3 In place of the 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt used in Example 3, dimethyl 5-sodium sulfoisophthalate was added in an amount of 1.5 mol% based on dimethyl terephthalate. Except that 0.112 parts of sodium acetate trihydrate (0.16 mol% relative to dimethyl terephthalate) is used as an ether formation inhibitor instead of tetraethylammonium hydroxide which is a thermal decomposition inhibitor. The same procedure as in Example 3 was performed. The results are shown in Table 2.

[0055]

Comparative Example 4 In place of the 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt used as the copolymerization component in Example 1, dimethyl 5-sodium sulfoisophthalate was added to dimethyl terephthalate 1: 1. 0.7 mol% of polyoxyethylene glycol having an average molecular weight of 1,000 is newly copolymerized with dimethyl terephthalate in an amount of 1.0% by weight, and tetraethyl hydroxide as a thermal decomposition inhibitor is further added. Example 1 was repeated except that 0.112 parts of sodium acetate trihydrate (0.16 mol% based on dimethyl terephthalate) was used as an ether formation inhibitor instead of ammonium. The results are shown in Table 2.

[0056]

Comparative Example 5 Instead of the 2,6-dicarbomethoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt used in Example 3, 3,5-dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt was replaced with dimethyl terephthalate. The same procedure as in Example 3 was carried out except that the amount used was 1.5 mol%. The results are shown in Table 2.

[0057]

EXAMPLE 12 The 75 denier / 24 filament copolyester yarn and the polyethylene terephthalate yarn obtained in Example 3 were each twisted and SZ twisted to 2.5.
00T / M was applied. A taffeta was woven using polyethylene terephthalate yarns as warp yarns and copolyester yarns as weft yarns. The basis weight was 147 g / m ² .

Next, this woven fabric was treated with a 3% aqueous sodium hydroxide solution at 100 ° C. to obtain a fabric having a weight loss rate of 20%.
Next, Cathilon Blue CD-FRLH /
Catilon Blue CD-FBLH = 1/1
(Hodogaya Chemical Co., Ltd.) 2% owf dyeing was carried out at 130 ° C. for 60 minutes in a dyeing bath containing Glauber's salt 3 g / L and acetic acid 0.3 g / L.

The obtained cloth was dyed in a vivid blue color only in the copolyester portion, and remained in white in the polyethylene terephthalate portion to give a high-quality color tone with a frosty tone. The texture was very good and the tear strength was high. It was a thing.

[0060]

[Table 1]

[0061]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location D03D 15/00 102 C 7199-3B D04B 1/16 7199-3B D06P 3/52 F 7306-4H 3 / 82 Z 7306-4H 3/854 7306-4H // D06M 101: 32

Claims (1)

[Claims] 1. A polyester having an ethylene terephthalate unit as a main repeating unit, wherein the dicarboxylic acid component (excluding organic phosphonic acid phosphonium salt) constituting the polyester is 0.5 in terms of phosphonium sulfonate base. To the amount of the following general formula (I): (In the formula, R ¹ and R ² are each independently a hydrogen _{atom, - (CH 2) n H} (n = 1~6 integer) or - (C
H ₂ ) _n OH (n = 1 to an integer of 6), R ₁ , R ₂ and R ₃
And R ₄ are the same or different groups selected from an alkyl group and an aryl group, and m is 1 or 2. ) A polyester fiber (A) made of a polyester obtained by copolymerizing a phosphonium salt of an organic sulfonic acid represented by the formula (1) and a polyester fiber (B) made substantially of polyethylene terephthalate, and being alkali-reduced. Polyester fabric that does.