JP2001254228A - Basic dye-dyeable copolyester fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester fiber which has high strength and a high elastic recovery (stretching property), having excellent dyeability with basic dyes, is suitable for sports wears, inner wears and the like, and is further suitable for uses blended or combined with other fibers. SOLUTION: This basic dye-dyeable copolyester fiber comprises a copolyester containing propylene terephthalate units as main constituting units and copolymerized with a basic dye-dyeing site component and at least one compound selected from the group consisting of aromatic dicarboxylic acid, aliphatic dicarboxylic acid and salicyclic dicarboxylic acid components, and has a Young's modulus of <=31 cN/dtex and an elongation recovery of >=80% on an elongation of 10%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a basic dyeable type copolyester fiber. Specifically, it is a fiber made of polyester with high elastic recovery (stretchability), high strength, and excellent dyeability of basic dyes.
The present invention relates to a dyeable basic polyester fiber which can be suitably used as sports clothing and inner clothing.

[0002]

2. Description of the Related Art Polyester fibers typified by polyethylene terephthalate have excellent mechanical strength, chemical resistance and the like, and are therefore widely used mainly for clothing and industrial purposes.

[0003] However, polyethylene terephthalate fiber has a low elongation elastic recovery rate and a low bending recovery rate, and thus has not been suitably used for applications requiring stretchability, such as innerwear, sports clothing, and pantyhose. Various proposals have been made to improve the stretchability.

One of them is that a polypropylene terephthalate fiber using 1,3-propylene glycol instead of ethylene glycol can increase the elongation elastic recovery rate and the flexural recovery rate in the prior art.
No. 320 is disclosed. However, this method can increase the elongation elastic recovery rate and the flexural recovery rate, but has insufficient dyeability, and cannot be dyed in a dark color at normal pressure.

Therefore, techniques for improving the dyeability under normal pressure are disclosed in JP-A-11-61562 and JP-A-11-6156.
No. 3 discloses this. These include polypropylene terephthalate and polyoxyalkylene glycol or aliphatic dicarboxylic acids having 12 or less carbon atoms, alicyclic dicarboxylic acids, isophthalic acid, and o-phthalic acid.
The seed is copolymerized in a specific amount to improve the dyeability under normal pressure. In these methods, it is possible to dye a deep color at normal pressure, but it is possible to dye only a disperse dye. Disperse dyes are inherently inferior in color development, and in these methods, development in fields requiring more sharpness is actually limited.

Regarding this problem, polyethylene terephthalate fibers can be dyed with a basic dye by copolymerizing an isophthalic acid component containing a metal sulfonate group as disclosed in Japanese Patent Publication No. 34-10497. There are known ways to do this. However, when polyethylene terephthalate is used as the basic skeleton as described above, it is difficult to impart the required stretchability.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems of the prior art, to have high elastic recovery (stretchability), high strength, and excellent dyeability of basic dyes. Suitable for sports clothing, inner clothing, etc., and when dyed with a disperse dye, there is a problem that the dye migrates to other fibers.However, there is no problem of migration sublimation in the basic dyeable type polyester. Accordingly, an object of the present invention is to provide a polyester fiber having a high commercial value, which is suitable for applications such as mixing and mixing with other fibers such as polyurethane.

[0008]

In order to solve the above-mentioned problems, propylene terephthalate is used as a main constituent unit, and a basic dye-dyeing seat component is contained in an amount of 0.1 to the total acid component.
And at least one compound selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids in an amount of 0.1 to 20 mol% based on the total acid components.
A fiber made of a polyester copolymerized by mol%, wherein the Young's modulus of the fiber is 31 cN / dtex or less.
It is characterized by a basic dye-dyeable copolyester fiber having an elongation elastic recovery of 80% or more at% elongation.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymerized polyester fiber of the present invention contains propylene terephthalate as a main constituent unit, and the basic dye-dyeing seat component is 0.1% to the total acid component.
1 to 10 mol% and at least one compound selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acid components are contained in an amount of 0.1 to 0.1% based on the total acid components.
It is a fiber made of a polyester copolymerized to ２０20 mol%.

The polyester of the present invention comprising propylene terephthalate as a main constituent unit is such that the acid component is terephthalic acid or an ester-forming derivative derived therefrom, and the glycol component is 1,1-propanediol; Examples thereof include 1,2-propanediol, 2,2-propanediol, and 1,3-propanediol. Among these glycol components, 1,3-propanediol is preferred from the viewpoints of stretchability and dyeability of the obtained fiber. The unit of propylene terephthalate in the polyester is preferably at least 70 mol%, more preferably at least 80 mol%, further preferably at least 85 mol%, from the viewpoint of elastic recovery.

The copolymerized polyester fiber of the present invention is used for improving the dyeability of a basic dye as described above.
It is a fiber comprising a polyester in which a basic dye-dyed seat component is copolymerized.

The basic dye-dyeing seat component of the present invention includes alkali metal salts of sulfoisophthalic acid, phosphonium salts of sulfoisophthalic acid and ester-forming derivatives derived therefrom. Specific examples thereof include alkali metal salts of sulfoisophthalic acid such as 5-sodium sulfoisophthalic acid and 5-lithium sulfoisophthalic acid, 5- (tetraalkyl) phosphonium sulfoisophthalic acid, and ester-forming derivatives derived therefrom. Can be Among these, 5-sodium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 5- (tetrabutyl) phosphonium sulfoisophthalic acid, and ester-forming derivatives derived therefrom are preferred from the viewpoint of dyeability.

The copolymerization amount of the basic dye-dyeing seat component is from 0.1 to 10 mol%, preferably from 0.2 to 7 mol%, based on the total acid component from the viewpoint of dyeability. More preferably, it is 0.3 to 5 mol%, and still more preferably 0.5 to 2 mol%. If the copolymerization amount is less than 0.1 mol%, the dyeability of the basic dye is poor, and if it exceeds 10 mol%, the dyeability is good but the fiber strength is poor.

Further, the copolymerized polyester fiber of the present invention comprises at least one kind selected from the group consisting of aromatic dicarboxylic acid, aliphatic dicarboxylic acid and alicyclic dicarboxylic acid together with the basic dye-dyeing seat component. Is a fiber comprising a polyester obtained by copolymerizing the compound of the formula (1).

By co-polymerizing at least one compound selected from the group consisting of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and an alicyclic dicarboxylic acid component, only a basic dye-dyed seat component is copolymerized. Compared with the polyester fiber thus prepared, the dyeability of the basic dye is excellent, and the copolymerization amount of the basic dye-dyeing seat component can be reduced, thereby improving the strength of the obtained fiber.

The aromatic dicarboxylic acid, aliphatic dicarboxylic acid and alicyclic dicarboxylic acid component in the present invention include, for example, aromatic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid and diphenoxyethanedicarboxylic acid. Alicyclic dicarboxylic acids such as aliphatic dicarboxylic acids such as dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid and dimer acid, 1,4-cyclohexanedicarboxylic acid and decalindicarboxylic acid And ester-forming derivatives derived therefrom. Among these dicarboxylic acid components, aliphatic dicarboxylic acids having 4 to 36 carbon atoms, such as adipic acid and dimer acid, and ester-forming derivatives derived therefrom are considered from the viewpoints of dyeability of basic dyes and fiber strength. Preferably, more preferably, 14 to 3 carbon atoms
6 aliphatic dicarboxylic acids and ester-forming derivatives derived therefrom.

In the present invention, the copolymerization amount of at least one compound selected from the group consisting of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and an alicyclic dicarboxylic acid component is as follows:
From the viewpoint of dyeability and strength, 0.1 to 20 with respect to all acid components
Mol%, preferably 0.5 to 15 mol%, more preferably 1 to 10 mol%, and still more preferably 2 to 5 mol%. If the copolymerization amount is less than 0.1 mol%, the fiber strength is low and the dyeability of the basic dye is inferior. on the other hand,
When the copolymerization amount exceeds 20 mol%, the effect of improving the dyeability reaches saturation, and conversely, the strength of the fiber deteriorates.

According to the present invention, as described above, polypropylene terephthalate contains at least one compound selected from the group consisting of a basic dye-dyeing seat component, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and an alicyclic dicarboxylic acid component. A fiber made of a copolymerized polyester, the alkali hydrolysis resistance of which is superior to a fiber obtained by copolymerizing the compound with polyethylene terephthalate. The same level of weight reduction processing is possible, and it is characterized by being excellent for use in blending with polyethylene terephthalate fiber or natural fiber.

In the copolyester fiber of the present invention, the content of dipropylene glycol in the polyester constituting the fiber is preferably a specific amount, from the viewpoint of heat resistance, elastic recovery, and mechanical properties, and more preferably Is 3% by weight
Or less, more preferably 2.8% by weight or less, further preferably 2.5% by weight or less, particularly preferably 2.3% by weight or less. If the dipropylene glycol content in the polyester exceeds the above range, heat resistance, elastic recovery, mechanical properties (such as strength) may be poor.

Further, the polyester constituting the copolymerized polyester fiber of the present invention has an increased filtration pressure during spinning during fiber production, which is presumed to be due to copolymerization of a basic dye-dyed seat component. -In view of the suppression of thread breakage or the suppression of dipropylene glycol by-produced during polyester production, the obtained polyester contains an alkali metal element in a range of 3 mol% or less based on all acid components of the obtained polyester. Preferably, more preferably 0.0
1-3 mol%, more preferably 0.05-2 mol%,
Particularly preferably, it is 0.1 to 1.5 mol%. If the content of the alkali metal element exceeds the above range, the effect of suppressing the increase in the filtration pressure and the breakage of the yarn during spinning when producing the fiber may be poor. As described above, the incorporation of an alkali metal element into the polyester is effective in increasing the filtration pressure during spinning and suppressing yarn breakage during fiber production. This is presumed to be the result of the interaction between the alkali metal element and the basic dyeing seat component. From this, the content of the alkali metal element in the polyester (mol%) / the amount of the basic dye-dyed seat component copolymerized with the polyester (mol%)
Is important, the content of alkali metal elements (mol%)
The ratio of the amount of the basic dye-dyed seat component (mol%) is 0.01
To 200, more preferably 0.01 to 10
0, more preferably 0.05 to 50. If this ratio exceeds the above range, the effect of suppressing the increase in filtration pressure and the breakage of yarn during spinning when producing fibers may be poor. Examples of a method for incorporating an alkali metal element into the polyester include a method of blending and adding a compound having an alkali metal element to the polyester. As the compound having an alkali metal element used in this case,
Compounds such as acetates, hydroxides, chlorides, alkoxides,
Examples thereof include acetates such as lithium acetate, sodium acetate and potassium acetate, hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and chlorides such as lithium chloride. In particular, it is preferable to add these compounds having an alkali metal element at an arbitrary stage in the reaction step of producing the polyester, and the compound may be used as a polyester reaction catalyst. These compounds may be added to the polyester such that the content of the alkali metal element in the polyester is 3 mol% or less based on all the acid components of the obtained polyester.

Further, the copolymerized polyester fiber of the present invention may further contain, in addition to the components constituting the copolymerized polyester, glycol components such as aliphatic glycols and alicyclic glycols, and polyoxyethylene glycols, as long as the object of the present invention is not impaired. Alkylene glycol and polyfunctional components can be copolymerized and contained.

The polyester constituting the copolymerized polyester fiber in the present invention can be produced by any method. For example, (1) a method for producing a polyester by transesterification of a dimethyl ester of a carboxylic acid with a glycol and a subsequent polycondensation reaction;
(2) A method of producing a polyester by an esterification reaction of a dicarboxylic acid and a glycol and a subsequent polycondensation reaction. At this time, at least one compound selected from the group consisting of a basic dye-dyeing seat component, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and an alicyclic dicarboxylic acid component, which is a copolymer component of the present invention, is described above. Added at any stage of the polyester reaction process,
It can be copolymerized.

As the catalyst used for the reaction of the polyester, a general reaction catalyst for producing a polyester can be used. For example, alkaline earth metals, metal compounds such as zinc, manganese, cobalt and titanium can be used as esterification and transesterification catalysts, and antimony, titanium and germanium compounds can be used as polycondensation reaction catalysts.

The copolyester fiber of the present invention must simultaneously satisfy the Young's modulus of the fiber of 31 cN / dtex or less, and the elastic recovery at 10% elongation of 80% or more. If the Young's modulus exceeds 31 cN / dtex, the softness of the texture, which is a feature of the present invention, is lost, and the Young's modulus is preferably 18 to 26 cN / dtex.
Further, if the elastic recovery rate at 10% elongation is less than 80%, the stretchability is lacking. Preferably it is 90% or more.

The copolymerized polyester fiber of the present invention comprises
From the viewpoint of texture, blending with other fibers, and the like, the fiber strength is preferably 2.4 cN / dtex or more, more preferably 2.5 cN / dtex or more, and still more preferably 2.6 cN / dtex.
N / dtex or more, particularly preferably 2.7 cN / dte
x or more.

Further, the copolymerized polyester fiber of the present invention comprises:
It contains pigments such as titanium oxide and carbon black, surfactants such as alkylbenzenesulfonate, conventionally known antioxidants, coloring inhibitors, light stabilizers, antistatic agents and the like within a range not to impair the object of the present invention. You may.

The copolyester fiber of the present invention can be produced by a conventionally known method. For example, 50
Melt spinning at a speed of 0 to 2500 m / min, then drawing,
A method of heat treatment, a method of melt-spinning at a speed of 1500 to 5000 m / min and simultaneously performing drawing and false twisting, or a method of performing false twisting after stretching, and melt-spinning at a high speed of 5000 m / min or more. Arbitrary thread-making conditions such as a method of omitting the stretching step can be adopted.

The cross-sectional shape of the copolyester fiber of the present invention may be irregular cross-section such as triangular, flat, multi-lobed, polygonal, H-shaped, and Π-shaped in addition to the round shape. Further, the filamentous form of the fiber,
Either filament or staple may be used, and is appropriately selected depending on the application.

The polyester fiber of the present invention can be used in the form of a fabric, such as a woven fabric, a knitted fabric, or a non-woven fabric, depending on its use.

Further, basic dyes for dyeing the polyester fiber of the present invention include 'Aizen Cathilon' (manufactured by Hodogaya Chemical Industry Co., Ltd.) and 'Kayacryl' (Nippon Kayaku Co., Ltd.).
'Estrol, Sumiacryl' (Sumitomo Chemical Co., Ltd.)
'Diacryl' (Mitsubishi Kasei Kogyo Co., Ltd.), 'Maxilon'
(Ciba-Geigy Co., Ltd.) and 'Astrazon' (Bayer Japan Co., Ltd.), but are not limited thereto. Dispersion-type basic dyes and disperse dyes can also be used. . Other dyes may be used in combination as long as the amount is within a range not to impair the effects of the present invention.

[0031]

The present invention will be described in more detail with reference to the following examples. In addition, each characteristic value in an Example was calculated | required by the following method. A. Intrinsic viscosity of polyester [η] An orthochlorophenol solution was determined at 25 ° C. B. Quantification of Dipropylene Glycol in Polyester ¹ H-NMR was measured using VARIAN UNITINOVA600, and quantification was performed based on the integral ratio of the obtained signals. C. Determination of alkali metal in polyester Polyester was hydrolyzed and quantified by atomic absorption spectrometry. D. Young's modulus, strength, elongation Using a Tensilon tensile tester manufactured by Toyo Baldwin Co., a value was determined from a stress-strain curve under the conditions of a test length of 20 cm and a tensile speed of 10 cm / min. E. FIG. Elongation elastic recovery rate The sample was measured using a constant speed elongation type tensile tester with a self-recording device.
1. Attach an initial load of 1/30 g per 1 dtex to a grip interval of 20 cm, and stretch to a predetermined elongation at a tensile speed of 10% of the grip interval. Immediately, the weight is removed at the same speed, and from the recorded stress-strain curve, α is a constant elongation to a predetermined elongation, and β is a recovery elongation reduced until the stress becomes equal to the initial load.

Elongation elastic recovery (%) = β / α × 100 Evaluation of Dyeing Property Two polyester fibers obtained were drawn and aligned to prepare a 24-gauge jersey cylinder, 2 g / l of “Sundet” G-29 (manufactured by Sanyo Chemical Co., Ltd.), 5 g / l of soda ash, “Detrol” WR-14 (manufactured by Meisei Chemical Industry Co., Ltd.) was refined in a treatment bath containing 2 g / l to obtain a dyed sample fabric. Further, the dyed sample fabric was used as a basic dye Malachite G.
Reen oxalate 5% owf, acetic acid (8
(0%) Dyeing was performed in a 0.5 cc / l bath at 110 ° C for 60 minutes (bath ratio 1: 100). Thereafter, the fabric was cooled, the knitted fabric was taken out, soaped, washed with air and dried, and the dye exhaustion rate was determined by the following formula. The higher the dye exhaustion rate, the better the dyeability.

Dye exhaustion rate = (617.2 of dye solution before dyeing)
Absorbance at nm-617.2 nm absorbance of dye solution after dyeing) /617.2 nm absorbance of dye solution before dyeing × 100 Example 1 87.1 parts by weight of dimethyl terephthalate, dimethyl adipate as aliphatic dicarboxylic acid component 4.2 parts by weight, 2.86 parts by weight of dimethyl 5-sodium sulfoisophthalate as a basic dye-dyeing seat component, and 73.4 parts by weight of 1,3-propanediol were used as transesterification catalysts, and tetrabutyl titanate 0 0.02 parts by weight, and 0.2 parts by weight of lithium acetate dihydrate as an alkali metal compound, and the temperature was raised over 4 hours while stirring to 140 to 230 ° C. to terminate the transesterification reaction. Phosphoric acid 0.03 parts by weight, tetrabutyl titanate 0.0
5 parts by weight were added. Next, a polycondensation reaction was carried out at a temperature of 250 ° C. under reduced pressure to obtain a polyester. Tables 1 and 2 show various conditions at this time and the obtained polyester properties.

After the obtained polyester is dried, a pore diameter of 0.3 mmφ is obtained at a spinning temperature of 260 ° C. by a usual melt spinning method.
A spinning take-off speed of 1800 m /
Minutes, spinning was performed, and undrawn was obtained. The obtained undrawn yarn was subjected to 1 HR at 60 ° C. for 2 hours using a normal hot roll drawing machine.
R 90 ° C, stretched at a stretch ratio of 3.1 times, and 83dtex2
A 4-filament drawn yarn was obtained. No increase in filtration pressure was observed during spinning (24 hours), and there was no yarn breakage. Table 2 shows the obtained fiber characteristics. Strength 2.6 cN / dtex,
Young's modulus 23.8 cN / dtex, elastic recovery 95%,
A fiber having a dye exhaustion rate of 91% and excellent strength, stretchability and dyeability was obtained.

Comparative Example 1 A polyester and a fiber were obtained in the same manner as in Example 1, except that neither the basic dye-dyeing seat component nor the aliphatic dicarboxylic acid component was used and no lithium acetate was added. . Tables 1 and 2 show various conditions, polyester obtained, and fiber properties at this time. Although the obtained copolyester fiber has good strength and elastic recovery, the basic dye has a very low exhaustion rate, and when the fiber after dyeing is washed with water, the basic dye is washed out and the dyeability is poor. Met.

Examples 2 to 11 and Comparative Examples 2 to 4 Polyesters and fibers were obtained in the same manner as in the Examples except that the types and amounts of the copolymer components and the types and amounts of the alkali metal compounds were changed. Tables 1 and 2 show various conditions, polyester obtained, and fiber properties at this time. Examples 2 to 11 are all within the scope of the present invention, and the strength, Young's modulus, elastic recovery of the obtained copolyester fiber,
Both dyeing properties were good.

On the other hand, Comparative Examples 2 to 4 were out of the scope of the present invention, and were inferior in polyester fiber properties. In Comparative Example 4, the filtration pressure increased during spinning (24 hours) (4.9).
MPa) was severe and thread breakage occurred frequently.

Comparative Example 5 93.5 parts by weight of dimethyl terephthalate, 4.5 parts by weight of dimethyl adipate as an aliphatic dicarboxylic acid component, 3.1 parts by weight of dimethyl 5-sodium sulfoisophthalate as a component for dyeing a basic dye, Ethylene glycol 6
Using 4 parts by weight of a transesterification reaction catalyst as a transesterification catalyst, 0.02 parts by weight of tetrabutyl titanate, and 0.2 parts by weight of lithium acetate dihydrate as an alkali metal compound;
The temperature was raised over 4 hours while stirring to 230 ° C. to terminate the transesterification reaction.
Parts by weight, and 0.05 parts by weight of tetrabutyl titanate were added. Next, a polycondensation reaction was performed at a temperature of 280 ° C. under reduced pressure to obtain a polyester. Tables 1 and 2 show various conditions at this time and the obtained polyester properties.

After drying the obtained polyester, a pore diameter of 0.3 mm was obtained at a spinning temperature of 290 ° C. by a usual melt spinning method.
A spinning take-off speed of 1800 m /
Minutes, spinning was performed, and undrawn was obtained. The obtained undrawn yarn was subjected to 1 HR at 85 ° C. for 2 hours using a normal hot roll drawing machine.
R120 ° C, stretched at 3.1 times the draw ratio, 83 dtex
A 24-filament drawn yarn was obtained. During spinning (24 hours)
No increase in filtration pressure was observed, and no yarn breakage occurred. Table 2 shows the obtained fiber characteristics. Strength 3.5cN / dte
x, Young's modulus 84cN / dtex, elastic recovery 55%
60% dye exhaustion, high Young's modulus, stretchability,
The dyeability was poor.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

The fiber obtained by the present invention has high strength, high elastic recovery (stretchability), excellent dyeability of basic dyes, is suitable for sports clothing, inner clothing, and the like. Suitable for applications such as blending and blending with fiber.

Claims (5)

[Claims] 1. A propylene terephthalate as a main constituent unit, wherein a basic dye-dyeing seat component is 0.1 to 10 mol% based on the total acid component, and aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid are used. A fiber comprising a polyester in which at least one compound selected from the group consisting of components is copolymerized with 0.1 to 20 mol% with respect to the total acid component, and the fiber has a Young's modulus of 31 cN / dtex.
A basic dye-dyeable copolyester fiber having an elongation elastic recovery of 80% or more at 10% elongation. 2. The basic dye according to claim 1, wherein the basic dye-staining component is at least one compound selected from the group consisting of alkali metal salts of sulfoisophthalic acid and phosphonium salts of sulfoisophthalic acid. Dyeable copolyester fiber. 3. The compound according to claim 1, wherein at least one compound selected from the group consisting of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and an alicyclic dicarboxylic acid component is an aliphatic dicarboxylic acid having 4 to 36 carbon atoms. 3. The dyeable basic polyester fiber of basic dye according to 2. 4. The polyester according to claim 1, wherein the content of dipropylene glycol in the polyester is 3% by weight or less.
Item 4. The dyeable basic polyester fiber of the basic dye. 5. The basic dyeable dye according to claim 1, wherein the content of the alkali metal element in the polyester is 3 mol% or less based on the total acid components of the obtained polyester. Polymerized polyester fiber.