JP2001055626A - Polyester fiber excellent in color development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject polyester excellent in alkaline hydrolysis resistance, light resistance, dye-affinity to cationic dyes and dispersion dyes and useful for woven and knit fabrics by constituting of a polyester containing a predetermined amount of a specific polyoxyalkylene glycol. SOLUTION: This polyester fiber excellent in color development comprises a polyester consisting of terephthalic acid as a main acid component and ethylene glycol as a glycol component and containing 0.1-10 wt.% of a compound expressed by the formula HO(CH2CH2O)l(RO)m(CH2CH2O)nH (R is a 3-25C aliphatic hydrocarbon; l and n satisfy 1<=l+n<=40; m is 2-50). The polyester fiber excellent in color development is preferably a polyester copolymerized with 0.1-10 mole % of a cation dyeable locus component such as sodium 5- sulfoisophthalate and the like. In addition to the compounds expressed by the formula, a polyester containing a polyoxyalkylene glycol component is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyester fiber. More specifically, the present invention relates to a polyester fiber having excellent dyeability, and more particularly, to a polyester fiber having good alkali hydrolysis resistance and light resistance, and having excellent coloring properties of a cationic dye and a disperse dye.

[0002]

2. Description of the Related Art Thermoplastic synthetic fibers typified by polyester and polyamide are excellent in mechanical strength, chemical resistance, heat resistance and the like, and are therefore widely used mainly for apparel use and industrial use.

[0003] However, these synthetic fibers are inferior in dyeability to disperse dyes and cationic dyes, and therefore have only economical and operational problems such as dyeing under high temperature and high pressure conditions and carrier dyeing. And has a quality defect that it is difficult to produce clear colors.

For this reason, Japanese Patent Publication No. 34-10497 proposes to copolymerize a compound having a dyeing site, such as 5-sodium sulfoisophthalic acid, with an aromatic polyester for the purpose of obtaining vivid coloration. Have been.
However, although this method improves the vivid coloration, the resulting polyester fiber has poor alkali hydrolysis resistance and thus has the following problems.

That is, when a polyester fiber copolymerized with the compound having a dyed seat is subjected to an alkali weight reduction treatment which is usually performed on a regular polyester fiber in order to improve the texture of the woven or knitted fabric, the dissolution rate with respect to alkali is reduced. However, compared to the regular polyester fiber, it was extremely large, and it was difficult to carry out a stable alkali weight reduction treatment, or the strength reduction after the alkali weight reduction treatment was extremely large, so that it was difficult to apply the alkali weight reduction processing.

To solve such a problem, Japanese Patent Laid-Open Publication No.
No. 6119 proposes a method of copolymerizing an ethylene oxide adduct of neopentyl glycol in order to improve the dyeing property. However, the effect of improving the dyeing property is not sufficient or the problem of a decrease in strength due to a decrease in melting point. There is.

Also, Japanese Patent Application Laid-Open Nos. 62-97914, 62-97915 and 62-979
In JP-A-16, in order to improve the alkali hydrolysis resistance of polyester fiber, 1,2- (4-
Method for copolymerizing carboxy) ethane component
Japanese Patent No. 37019 proposes a method of copolymerizing dimer diol with polyester.

[0008] However, in these methods, although the alkali hydrolysis resistance is slightly improved, the dyeability is reduced, so that a polyester fiber satisfying both the alkali hydrolysis resistance and the dyeability can be obtained at all. Did not.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems of the prior art, improve alkali hydrolysis resistance and light resistance, and excel in dyeing properties of cationic dyes and disperse dyes. An object of the present invention is to provide a polyester fiber having a high commercial value, which is suitable for applications such as blending and blending with polyester fibers.

[0010]

In order to solve the above-mentioned problems, the present invention provides terephthalic acid as a main acid component,
A polyester containing ethylene glycol as a main diol component and having a general formula of HO (CH ₂ CH ₂ O) l
(RO) it is an _{m (CH 2 CH 2 O)} nH wherein excellent polyester fiber compound chromogenic consisting 0.1-10 wt% containing polyester represented by (I). (Wherein, R is an aliphatic hydrocarbon group having 3 to 25 carbon atoms, l and n are the same or different integers, and 1 ≦ l + n
≦ 40, m is an integer of 2 to 50 and may be the same or different. )

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION
A polyester having terephthalic acid as a main acid component and ethylene glycol as a main diol component, and having a general formula of HO (CH ₂ CH ₂ O) l (RO) m (CH ₂
The CH ₂ O) compound represented by the nH (I) 0.1 to 1
It is a polyester containing 0% by weight. (However, in the formula,
R is an aliphatic hydrocarbon group having 3 to 25 carbon atoms, l and n are the same or different integers and 1 ≦ l + n ≦ 40, and m is 2 to 50.
It may be the same or different in the integers up to. The polyester fiber containing the compound represented by the general formula (I) has improved alkali hydrolysis resistance and light resistance, and has excellent dyeability with respect to cationic dyes and disperse dyes.

In the compound of the present invention represented by the general formula (I), R in the formula is an aliphatic hydrocarbon group having 3 to 25 carbon atoms, preferably 3 to 20, more preferably 3 to 15 carbon atoms.
It is. When R is less than 3, the alkali hydrolysis resistance is poor. When R exceeds 25, the light resistance and the strength of the obtained fiber are inferior. Further, from the viewpoint of alkali hydrolysis resistance, the number of moles m of the oxide of R is 2 to 50, preferably 5 to 5.
-40, more preferably 10-30. When m is less than 2, the dyeability is poor. On the other hand, when m exceeds 50, light resistance and alkali hydrolysis resistance are poor. In the formula, specific examples of R include a propylene group, a pentamethylene group, a hexamethylene group, a 1-methyl-ethylene group, and a 3-methyl-1,5
-Pentamethylene group, 2,2-dimethyl-1,3-propylene group, 2-butyl-2-ethyl-1,3-propylene group, 4,4'-diphenylene-2,2-propane group and the like. R is preferably a 1-methyl-ethylene group from the viewpoint of dyeability and alkali hydrolysis resistance.

In the compound of the present invention represented by the general formula (I), l and n are integers, and the obtained fiber has a light fastness in order to have both alkali hydrolysis resistance and dyeing properties. L + n is from 1 to 40, preferably from 2 to 30, more preferably from 3 to 20, from the viewpoints of properties, alkali hydrolysis resistance, dyeability and the like. When l + n is less than 1, the effect of improving the dyeability is small. On the other hand, when it exceeds 40, not only the alkali hydrolysis resistance of the obtained fiber is inferior, but also the mechanical properties such as strength are inferior.

The content of the compound represented by the general formula (I) of the present invention is from 0.1 to 10% by weight, preferably from 0 to 10% by weight, from the viewpoints of the light resistance, alkali hydrolysis resistance and dyeability of the obtained fiber. 0.5 to 8% by weight, more preferably 1 to 7% by weight. When the content is less than 0.1% by weight, the effect of improving the dyeability is small. If it exceeds 10% by weight, not only the alkali hydrolysis resistance of the obtained fiber is poor, but also the mechanical properties such as strength are poor.

The polyester in the present invention is mainly intended for polyethylene terephthalate containing terephthalic acid as a main acid component and ethylene glycol as a main diol component.

In the polyester of the present invention, a cationically dyed seat component is preferably copolymerized in order to improve the dyeability of the cationic dye. Examples of the cationic dyeing seat component include alkali metal salts of sulfoisophthalic acid, phosphonium salts of sulfoisophthalic acid, and ester-forming derivatives derived therefrom. Specifically, 5-sodium sulfoisophthalic acid,
Examples thereof include alkali metal salts of sulfoisophthalic acid such as 5-lithium sulfoisophthalic acid, 5- (tetraalkyl) phosphonium sulfoisophthalic acid, and ester-forming derivatives derived therefrom. Among them, sodium salt, lithium salt and (tetraalkyl) phosphonium salt of 5-sulfoisophthalic acid are preferable from the viewpoint of dyeing property, and 5-lithium sulfoisophthalic acid is more preferable.

The amount of copolymerization of the cationically dyed seat component is preferably from 0.1 to 10 mol%, more preferably from 0.1 to 10 mol%, based on the total acid component, from the viewpoint of improving the dyeability and the resistance to alkali hydrolysis. 2 to 7.0 mol%, and more preferably 0.1 to 7.0 mol%.
5 to 5.0 mol%, particularly preferably 1.0 to 4.0 mol%.
0 mol%.

Further, the polyester of the present invention preferably contains a polyoxyalkylene glycol such as polyethylene glycol and polypropylene glycol in order to improve the dyeability. Among these glycol components, polyethylene glycol is particularly preferred from the viewpoint of dyeability and mechanical properties. The content of polyethylene glycol is preferably from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, from the viewpoint of dyeability.

The polyester of the present invention can be a copolymerized polyester obtained by copolymerizing a dicarboxylic acid component and a glycol component other than the dicarboxylic acid component and the glycol component constituting the polyester as long as the quality of the polyester is not impaired.

Examples of the dicarboxylic acid component and glycol component to be copolymerized include acid components such as aromatic dicarboxylic acid, aliphatic dicarboxylic acid and alicyclic dicarboxylic acid, and aromatic glycol, aliphatic glycol and alicyclic glycol. Glycol components can be mentioned.
Specifically, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, etc. Alicyclic dicarboxylic acids such as aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acids, and decalin dicarboxylic acids, and ester-forming derivatives derived therefrom. Among these dicarboxylic acid components, terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and ester-forming derivatives derived therefrom,
Aliphatic dicarboxylic acids such as adipic acid, sebacic acid and dimer acid and ester-forming derivatives derived therefrom are preferred in view of the dyeability of disperse dyes and cationic dyes.

The glycol components include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, Examples thereof include aliphatic glycols such as neopentyl glycol, alicyclic glycols such as 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, and hydrogenated bisphenol A.

The polyester of the present invention further comprises, in addition to the above-mentioned copolymer components, β-hydroxyethoxybenzoic acid,
a hydroxydicarboxylic acid component such as p-oxybenzoic acid,
Further, a copolymer of a polycarboxylic acid component and / or a polyol component such as trimellitic anhydride, benzophenonetetracarboxylic acid, trimethylolpropane, glycerin, and pyromellitic anhydride may be used.

The above dicarboxylic acid component, glycol component and the like may be used alone or in combination of two or more. The amount of the copolymer component is preferably 20 mol% or less from the viewpoint of mechanical properties such as strength of the obtained fiber, alkali hydrolysis resistance, dyeability and the like.

The polyester of 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 terephthalic acid with ethylene glycol and a subsequent polycondensation reaction, and (2) a method of producing a polyester by an esterification reaction of terephthalic acid with ethylene glycol and a subsequent polycondensation reaction. A method for producing the composition can be used. At this time, the compound represented by the general formula (I) of the present invention can be added at any stage of the above-mentioned polyester reaction step and polycondensed.

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

The polyester of the present invention and a fiber comprising the same may be used as pigments such as titanium oxide and carbon black, a surfactant such as an alkylbenzene sulfonate, a conventionally known antioxidant, and a coloring agent as long as the object of the present invention is not impaired. It may contain an inhibitor, a light stabilizer, an antistatic agent and the like.

The polyester fiber of the present invention can be produced by a conventionally known method. For example, 500-2
Melt spinning at a speed of 500 m / min, followed by stretching and heat treatment; melt spinning at a speed of 1500 to 5000 m / min; simultaneous stretching or false twisting; Melt spinning at a high speed of
Depending on the application, any yarn-making conditions such as a method of omitting the stretching step can be adopted.

The cross-sectional shape of the polyester fiber of the present invention is not limited to a circle, but may be a triangular, flat, multi-lobed, polygonal, H-shaped, or Π-shaped cross section. 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.

Examples of the method of reducing the weight of the polyester fiber of the present invention include a plasma treatment, a laser treatment, and an alkali weight reduction treatment. Is preferably alkali reduction treatment. The alkali used at this time is Na
Compounds such as OH, KOH, and LiOH can be mentioned. The weight reduction treatment of polyester fibers and the like is performed with the aqueous solution of alkali, and the alkali concentration is preferably 0.5 to 10% by weight. In this case, the alkali weight reduction rate is particularly limited. The weight loss rate is 50% from the viewpoint of the strength, texture, etc. of the obtained fiber.
Is preferably 30% or less, more preferably 20% or less.

Further, as cationic dyes for dyeing the polyester fiber of the present invention, "Aizen Cathilon" (manufactured by Hodogaya Chemical Industry Co., Ltd.), "Kayacryl" (manufactured by 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.) may be used. However, the dye is not limited thereto, and a dispersible cationic dye or a disperse dye may 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.

[0032]

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. Thermal properties of polyester Glass transition temperature (Tg), melting point (Tm) of polyester
Was measured at a heating rate of 16 ° C./min using a DSC7 apparatus manufactured by PerkinElmer. C. Strength and elongation Using a Tensilon tensile tester manufactured by Toyo Baldwin Co., values were obtained from a stress-strain curve under the conditions of a test length of 20 cm and a tensile speed of 10 cm / min. D. 3 g of each of the alkali-hydrolysis-resistant polyester fibers was weighed and heated at 98 ° C.
The weight after the treatment in a 3% aqueous solution of NaOH for 3 minutes was measured, and the weight loss rate during the alkali treatment was determined and used as an index of the alkali hydrolysis resistance. The greater the weight loss rate during the alkali treatment, the lower the alkali hydrolysis resistance. The alkali weight loss rate is
30% or less was accepted.

Alkali treatment weight loss rate (%) = (weight before weight loss−weight after alkali weight loss) / weight before weight loss × 100 Evaluation of Dyeing Properties Two obtained 75d-36F polyester fibers were drawn together to prepare a 24-gauge sheet of cotton, and "Sundet" G-
29 (manufactured by Sanyo Chemical Co., Ltd.) 2 g / l, soda ash 5 g /
1, "Detrol" WR-14 (Meisei Chemical Industry Co., Ltd.)
Scouring) in a treatment bath containing 2 g / l. After drying, intermediate heat setting was performed at 170 ° C. to obtain a dyed sample fabric.

Further, the above-mentioned dyed sample fabric was treated with the cationic dye Malachite Green oxalate 3% ow.
f, acetic acid (80%) as an auxiliary agent in a 0.5 cc / l bath
Dyeing was carried out at 0 ° C. for 60 minutes (bath ratio 1: 100). After cooling, taking out the knitted fabric and soaping, washing with water and drying in air,
The dye exhaustion rate was determined by the following equation.

Dye exhaustion rate = (617 nm of dye solution before dyeing)
Absorbance at 617 nm of dye solution after dyeing) / absorbance at 617 nm of dye solution before dyeing × 100 The higher the dye exhaustion rate, the better the dyeability. The rate needs to be 70% or more. Example 1 93.2 parts by weight of dimethyl terephthalate, 2.9 parts by weight of dimethyl 5-sodium sulfoisophthalate as a cationic dyeing seat component, 60 parts by weight of ethylene glycol, and lithium acetate dihydrate 0.1 as a transesterification catalyst
5 parts by weight and stirring to 140 to 235 ° C.
The temperature was raised over a period of time to perform a transesterification reaction. After the transesterification reaction was completed, the compound represented by the general formula (I) in which R was a 1-methyl-ethylene group, m = 30, and l + n = 4 was replaced with 5
Then, 0.04 parts by weight of trimethyl phosphate as a coloring inhibitor and 0.04 parts by weight of antimony trioxide as a polycondensation reaction catalyst are added, and the polycondensation reaction is carried out at a temperature of 290 ° C. under reduced pressure according to a conventional method. Was carried out to obtain a polyester. Table 1 shows the conditions at this time and the properties of the obtained polyester.

Next, after drying the obtained polyester, it was supplied to a spinning machine, melted by a melter, weighed, discharged from the spin pack, and taken up at a speed of 1300 m / min.
After drawing the obtained undrawn yarn 2.80 times at 80 ° C.,
Heat set on roller (130 ° C), 75 denier 36
A drawn filament was obtained. Table 2 shows the obtained fiber properties and results. Weight loss rate during alkali treatment is 25
%, And the dye exhaustion rate was as good as 80%. Comparative Example 1 A polyester and a fiber were obtained in the same manner as in Example 1 except that the compound represented by the formula (I) was not contained.
The obtained polyester and fiber properties are shown in Tables 1 and 2. The obtained polyester fiber was inferior in alkali hydrolysis resistance and dyeability. Examples 2 to 15, Comparative Examples 2 and 3 Polyesters and fibers were obtained in the same manner as in Example 1 except that R, l, m, n and the amount of the compound represented by formula (I) were changed. . The obtained polyester and fiber properties are shown in Tables 1 and 2. In all of Examples 2 to 15, the alkali hydrolysis resistance and the dyeability of the obtained polyester fiber were good within the scope of the present invention. on the other hand,
In Comparative Example 2, the compound represented by the general formula (I) was out of the range of the present invention (m = 1), and the fiber was poor in alkali decomposition resistance and dyeability. Comparative Example 3 did not contain the compound represented by the general formula (I) and used polyethylene glycol, but was inferior in alkali decomposition resistance.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

The polyester fiber obtained according to the present invention has alkali hydrolysis resistance, light resistance, cationic dye,
Excellent dyeability for disperse dyes.

Claims (4)

[Claims] 1. A polyester comprising terephthalic acid as a main acid component and ethylene glycol as a main diol component and having a general formula of HO (CH ₂ CH ₂ O) l (R
_{O) m (CH 2 CH 2} O) nH (I) color excellent in polyester fiber compound consists of 0.1 to 10 wt% containing polyester represented by. (Where R is
The aliphatic hydrocarbon group having 3 to 25 carbon atoms, l and n are the same or different integers and 1 ≦ l + n ≦ 40, and m is an integer of 2 to 50 and may be the same or different. ) 2. The polyester fiber having excellent color developability according to claim 1, which is a polyester obtained by copolymerizing a cationically dyed seat component with 0.1 to 10 mol%. 3. The chromogenic property according to claim 2, wherein the cationic dyeing seat component is at least one component selected from the group consisting of lithium salt, sodium salt and (tetraalkyl) phosphonium salt of 5-sulfoisophthalic acid. Excellent polyester fiber. 4. The polyester according to claim 1, wherein the polyester is a polyester containing a polyoxyalkylene glycol component in addition to the compound represented by the general formula (I) according to claim 1. Polyester fiber with excellent coloring.