JPH07118924A - Phosphorus-containing polyester fiber, cloth and dyeing thereof - Google Patents

Abstract

PURPOSE:To obtain the polyester fiber cloth having a high strength retention both before and after dyeing by dyeing a copolymer of ester containing ethylene terephthalate units with a specific amount of phosphorus compound under specific dyeing conditions. CONSTITUTION:An ester containing ethylene terephthalate units is copolymerized with one or more of phosphorus compounds selected from the groups of formulas I (R<1>-R<3> are H, monovalent organic group of 1 to 18 carbon atoms), II (R<4> is a monovalent organic group of 1 to 18 carbon atoms) and III (R<5> is a monovalent ester-forming group; A is a divalent organic group of 1 to 18 carbon atoms; the compound forms intra-molecular anhydride ring) in an mount of 0.05 to 4wt.% as a phosphorus element to give a phosphorus-containing polyester fiber. The cloth of this polyester fiber is dyed with a dispersion dye in a dye bath which pH is buffered to 5-6.5 and contains an acetate salt of an amine such as n-butyl-amine to give the brightly died cloth having higher than 80% of the strength retention before and after dyeing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphorus-containing polyester fiber having a high strength retention before and after dyeing, a cloth made of the fiber and a dyeing method thereof, and more specifically, phosphoric acid and phosphonic acid in the polyester main chain. , A fiber or a cloth made of polyester in which phosphinic acid or a derivative thereof is copolymerized and having a high strength retention before and after dyeing, it is possible to improve the flame retardancy and anti-pill property of a conventional phosphorus compound. The application can be further expanded.

[0002]

2. Description of the Related Art Polyester fibers have hitherto been used in various fields such as clothes, interiors, stuffed cotton and non-woven fabrics because of their excellent mechanical properties and workability. Various functions such as dyeability, flame retardancy, anti-pill property, hygroscopicity, and antistatic property are required according to the spread of its applications, and modifiers are applied by copolymerization, kneading, and post-processing. Polyester fibers have been modified by applying them by means such as. Normal,
Phosphorus compounds are often used as such modifiers, especially for imparting properties such as flame retardancy, dyeability, and anti-pill property. For example, Japanese Examined Patent Publication No. 47-22334 proposes improvement of dyeability by adding an isophthalic acid component having a quaternary phosphonium sulfonate group.
No. 9 proposes imparting flame retardancy by adding a phosphinic acid derivative. Further, JP-A-55-112313 proposes a method for copolymerizing phosphoric acid and JP-A-63-135517 for copolymerizing an alkyl ester of phosphoric acid to exhibit anti-pill property.

[0003]

As described above, phosphorus compounds are often used as modifiers, but when phosphoric acid, phosphonic acid, phosphinic acid, and their derivatives are used as modifiers, The resulting fiber had the drawback of being susceptible to hydrolysis. This is because the phosphate ester bond has a stronger reaction activity than the carboxylic acid ester bond, and is essentially inevitable.
Fibers that are easily hydrolyzed in this way have a limitation in the development of applications because they cause a decrease in strength due to a decrease in the degree of polymerization due to hydrolysis during the dyeing process. The present invention provides a method for dyeing a polyester fiber obtained by copolymerizing phosphoric acid, phosphonic acid, phosphinic acid and its derivatives which are susceptible to hydrolysis with a minimum reduction in strength due to hydrolysis, and a dyed fiber obtained by the method. And to provide a fabric.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that if the pH of the dyeing bath solution is set to 5.0 to 6.5 and an amine acetate salt is allowed to coexist. ,
The inventors have found that the degree of polymerization of the polyester fiber is small and the strength can be maintained, and finally the present invention has been completed.
That is, in the present invention, the main constitutional unit is ethylene terephthalate, and 0.05 to 4.0% by weight, as a phosphorus element, one or more kinds selected from the phosphorus compounds represented by the following general formulas 4, 5, and 6 Phosphorus-containing polyester fiber characterized by having a strength retention rate of 80% or more before and after dyeing, which is a fiber made of copolymerized polyester, and a cloth made of the fiber, and a pH of a dyeing solution when dyeing them.
Is maintained at 5.0 to 6.5, and an amine acetate is present in the dye liquor, which is a method for dyeing a phosphorus-containing polyester fiber or cloth.

[0005]

[Chemical 4]

[0006]

[Chemical 5]

[0007]

[Chemical 6] (Wherein R ¹ , R ² , and R ³ are hydrogen atoms or monovalent organic groups having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
18 is a monovalent organic group, R ⁵ is a monovalent ester-forming functional group, A is a divalent organic group having 1 to 18 carbon atoms, and the compound represented by Chemical formula 3 is a cyclic anhydride in the molecule. May be formed. )

The present invention will be described in detail below. First, in the polyester fiber of the present invention, 75 mol% or more of the repeating constitutional unit is ethylene terephthalate, and its raw material components are terephthalic acid or dimethyl terephthalate and ethylene glycol. As the copolymerization component, one or more selected from the phosphorus compounds represented by the general formulas 4, 5, and 6 may be used. In addition, isophthalic acid, 2,6-
Aromatic dicarboxylic acids such as naphthalene dicarboxylic acid and 5-sodium sulfoisophthalic acid and their derivatives, adipic acid, sebacic acid, azelaic acid, hexahydroterephthalic acid and other aliphatic dicarboxylic acids and their derivatives, trimethylene glycol, tetramethylene glycol It is also possible to use glycols such as, neopentyl glycol, 1,4-cyclohexanediol, etc., or mixtures thereof. Such polyester is synthesized by a conventionally known method. For example, by directly esterifying terephthalic acid and ethylene glycol, transesterifying a lower alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol, or reacting terephthalic acid with ethylene oxide. , An ethylene glycol ester of terephthalic acid and / or a low polymer thereof are produced, and then the phosphorus compound is added, and the polycondensation reaction is performed by heating under reduced pressure to a desired degree of polymerization. The compound may be added at any time, and may be added to the slurry tank of terephthalic acid and ethylene glycol.

The polyester fiber used in the method of the present invention is copolymerized with one or more selected from the phosphorus compounds represented by the above-mentioned general formulas 4, 5, and 6. Examples of the compound represented by the general formula 4 include phosphoric acid, monomethyl phosphate, monoethyl phosphate, diethyl phosphate,
Trimethyl phosphate, triphenyl phosphate, monomethyl monoethyl phosphate, tri (β-hydroxy) ethyl phosphate, mono (β-hydroxy) ethyl phosphate, di (β-hydroxy) ethyl phosphate and the like can be mentioned. Moreover, you may use those mixtures.

Examples of the compound represented by the general formula 5 are phenylphosphonic acid, methylphosphonic acid, dimethylmethylphosphonate, diphenylmethylphosphonate, monomethyl phenylphosphonate, monoethyl phenylphosphonate, di (β-hydroxy) ethyl methylphosphonate and phenylphosphone. Di (β-hydroxy) ethyl acid and the like,
Mixtures thereof may be used.

Further, as the compound represented by the general formula 6, (2-carboxyethyl) methylphosphinic acid,
(2-carboxyethyl) phenylphosphinic acid, (2
-Methyl methoxycarbonylethyl) methylphosphinate, ethyl (2-ethoxycarbonylethyl) phenylphosphinate, (2-hydroxyethoxycarbonylethyl) phenylphosphinic acid and its ethylene glycol ester, (2-methoxycarbonylethyl) hexylphosphinic acid, 2-methyl-2,5-dioxo-1
-Oxa-2-phosphorane, 2-phenyl-2,5-dioxo-1-oxa-2-phosphorane and the like,
Mixtures thereof may be used.

The polyester compound used in the present invention contains the above phosphorus compound as a phosphorus element in an amount of 0.05 to 4.
0% by weight is copolymerized. The amount of copolymerization varies depending on the purpose of its modification, but when it is used as a flame retardant, it is preferably 0.3 to 1.0% by weight. If the amount of copolymerization is smaller than this, the effect as a modifier is not sufficient, and conversely, if it is large, the excellent physical properties inherent in polyester are impaired, which is not preferable.

Regarding the method for producing the above phosphorus-containing polyester fiber, a conventionally known method can be adopted, and the cross-sectional shape of the fiber can be circular, polygonal, star-shaped, hollow or the like. The obtained polyester fiber can be used as a filament or a staple by subjecting it to a drawing heat treatment, a false twist, and a crimping process, if necessary. Further, composite spinning with other polyester, polyethylene, etc. is also possible. Fabrics are made using the obtained fibers,
The types of cloth include woven and knitted fabrics, and examples of the woven structure include plain weave, twill weave, and satin weave. Examples of knits include tricot and jersey,
The fabric of the present invention can employ any type of fabric.

Next, as a method for dyeing the polyester fiber and the cloth obtained by the above-mentioned method, the dyeing temperature of the polyester fiber is usually 120 to 140 ° C. when dyeing with a disperse dye. The pH is kept at about 4 to stabilize the dye, but under these conditions, in the case of the phosphorus-containing polyester, as mentioned above, the strength is lowered due to hydrolysis, and the pH of the dye liquor is also lowered. Therefore, there was a problem in the uniformity of dyeing. Therefore, in the dyeing method of the present invention, it is necessary to maintain the pH of the dyeing liquor at 5.0 to 6.5, preferably 5.4 to 6.0, and to make the amine acetate salt present.

The pH of the dyeing solution is acetic acid / sodium acetate solution,
It can be prepared with a buffer solution such as an aqueous solution of potassium dihydrogenphosphate / dipotassium hydrogenphosphate. pH
When the value is higher than 6.5, the dye deteriorates and the color of the dyed product becomes dull. On the other hand, if it is lower than 5.0, the desired suppression of hydrolysis cannot be achieved, and the strength of the fiber decreases, which is not preferable. In addition, the amine acetate was added to the dye bath solution at 5.
It is preferably added at a concentration of 0 × 10 ^{−3 to} 15.0 × 10 ⁻³ mol / l. If the concentration is low, the effect will be insufficient, and if it is high, decomposition by amine will occur as a side reaction and the strength of the fiber will decrease, which is not preferable. The amine type is preferably strongly basic, and the alkylamine is particularly preferable because it has a pKa of 10 to 11 and is highly basic. Specific examples thereof include ethylamine, diethylamine, triethylamine, n-butylamine, cyclohexylamine, aniline and pyridine. The acid that forms a salt with the amine may be a weak acid, but acetic acid is preferred because it does not affect the dyeability. In the present invention, the pH is 5.0 to
Adjusting to 6.5 and adding the amine acetate alone are effective, but it is surprising that a sufficient effect can be obtained by combining the two.

[0016]

As described above, the conventional phosphorus-containing polyester is hydrolyzed to cleave the highly reactive phosphoric acid ester moiety to generate a phosphoric acid residue, and the phosphoric acid residue has a catalytic action and a carboxyl group. Although the acid ester portion was also cut to eventually weaken the strength of the fiber or cloth, the reason why the strength of the fiber or cloth of the present invention is maintained is that the pH is 5 to 6.5.
Keeps the phosphoric acid ester moiety from being cleaved, further adding an amine acetate to cause an exchange reaction with the strong acid phosphoric acid and inactivating the phosphate residue to suppress hydrolysis. It seems that they are doing.

[0017]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight", and each physical property value was measured by the following methods. Intrinsic viscosity [η]: Measured at 30 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 3: 2). Dyeing sharpness: It was visually observed with the naked eye and evaluated in three grades of ◯, Δ, and ×. Strength retention before and after dyeing: The breaking strength after dyeing is expressed in% with respect to the breaking strength before dyeing, and the breaking strength is "tensilon".
UTM-4L type tensile tester (Toyo Baldwin Co., Ltd.)
Manufactured), with a gauge length of 200 mm and an initial load of 1/30 g /
d, extend the sample at an extension speed of 200 mm and record at a recording speed of 50
The breaking strength of the fiber was calculated from the SS curve drawn at 0 mm / min and calculated. Ester bond decomposition rate before and after dyeing: Expressed as a change (% BB) in [η] obtained by the following formula. % B. B. = 0.244 × {[η] f ^-1.781 − [η] i
^-1.471 }

Production Example 1 1297 parts of terephthalic acid and 1067 parts of ethylene glycol were charged into a stainless steel autoclave equipped with a stirrer, a distillation column, a pressure regulator and a thermometer, and further 3.2 ml of triethylamine and 0.55 part of antimony trioxide were added. Was added and the esterification reaction was carried out for 2 hours while successively removing water produced by esterification from the system at 230 ° C. and a gauge pressure of 2.5 kg / cm ² . To this reaction product, 11 parts of a mixture of monoethyl phosphate / diethyl phosphate (53:47) was added, and the mixture was stirred at 230 ° C for 20 minutes. Then, the temperature of the system was raised to 275 ° C. in 1 hour, the pressure of the system was gradually reduced to 0.1 mmHg during this time, and polycondensation was performed for 1 hour under these conditions. The obtained polymer [η] was 0.57 and the phosphorus content was 1350 ppm. This polymer was melt-spun and drawn by a conventional method, and the obtained yarn was used as a knitted fabric, which was designated as Sample A.

Production Example 2 1236 parts of terephthalic acid and 1055 parts of ethylene glycol were charged into a stainless steel autoclave equipped with a stirrer, a distillation column, a pressure regulator and a thermometer, and further 3.2 ml of triethylamine and 0.55 part of antimony trioxide were added. Was added and the esterification reaction was carried out for 2 hours while successively removing water produced by esterification from the system at 230 ° C. and a gauge pressure of 2.5 kg / cm ² . 46 parts of phenylphosphonic acid was added to this reaction product, and the mixture was stirred at 230 ° C. for 20 minutes. Subsequently, the temperature of the system was raised to 275 ° C. in 1 hour, during which the system pressure was gradually reduced to 0.1 mmHg, and polycondensation was performed for 2 hours under these conditions. [Η] of the obtained polymer
Was 0.62 and the phosphorus content was 5200 ppm.
This polymer was melt-spun and drawn by a conventional method, and the obtained yarn was used as a knitted fabric, which was designated as Sample B.

Production Example 3 1236 parts of terephthalic acid and 1055 parts of ethylene glycol were charged into a stainless steel autoclave equipped with a stirrer, a distillation column, a pressure adjuster and a thermometer, and further 3.2 ml of triethylamine and 0.55 part of antimony trioxide. Was added and the esterification reaction was carried out for 2 hours while successively removing water produced by esterification from the system at 230 ° C. and a gauge pressure of 2.5 kg / cm ² . To this reaction product was added 62 parts of (2-carboxyethyl) phenylphosphinic acid,
Stirred at 0 ° C. for 20 minutes. Then, the system temperature is increased to 2 in 1 hour.
The temperature was raised to 75 ° C., during which the system pressure was gradually reduced to 0.1 mmHg, and polycondensation was carried out for 2 hours under these conditions. The obtained polymer [η] was 0.64 and the phosphorus content was 5900 ppm. This polymer is melt-spun and drawn by a conventional method, and the obtained yarn is used as a knitted fabric,
This was designated as Sample C.

Examples 1 to 3 The knitted fabrics of Samples A to C obtained in Production Examples 1 to 3 were dyed under the following conditions, and after dyeing, reduction washing was performed according to a conventional method. Dye liquor composition; Dianix Blue AC-E 1.0
% Owf Disper TL 1 g / l acetic acid 0.2 N / sodium acetate 0.2 mol / l buffer solution (p
H = 5.6) Cyclohexylamine acetate 6.0 × 10 ⁻³ mol / l Bath ratio; 1: 100 Temperature × hour 130 ° C. × 1 hour

Examples 4 and 5 and Comparative Examples 1 to 4 In Examples 1 to 3, except that the amine species of acetate shown in Table 1 were used instead of cyclohexylamine acetate and the pHs shown in Table 1 were used, respectively. Samples A to C were dyed in the same manner as in Examples 1 to 3. The results are also shown in Table 1.

[0023]

[Table 1]

[0024]

As is clear from Table 1, according to the method of the present invention, fibers and cloths having good dyeing sharpness, high strength retention of 80% or more, and low ester bond decomposition rate can be obtained. You can see that That is, according to the present invention, since fibers and cloths that have been conventionally modified with a phosphorus compound are dyed clearly without being adversely affected by the phosphorus compound, it can be used not only in the field of clothing but also in interiors, industrial materials, etc. It is possible to dramatically expand the field and contribute to the industrial world.

Claims (3)

[Claims] 1. A main constituent unit is ethylene terephthalate, and at least one selected from phosphorus compounds represented by the following general formulas 1, 2, and 3 is 0.0 as a phosphorus element.
A phosphorus-containing polyester fiber characterized by having a strength retention before and after dyeing of 80% or more, which is a fiber made of polyester copolymerized by 5 to 4.0% by weight. [Chemical 1] [Chemical 2] [Chemical 3] (Wherein R ¹ , R ² , and R ³ are hydrogen atoms or monovalent organic groups having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
18 is a monovalent organic group, R ⁵ is a monovalent ester-forming functional group, A is a divalent organic group having 1 to 18 carbon atoms, and the compound represented by Chemical formula 3 is a cyclic anhydride in the molecule. May be formed. ) 2. A fabric made of the phosphorus-containing polyester fiber according to claim 1. 3. A main constituent unit is ethylene terephthalate, and at least one selected from the phosphorus compounds represented by the above general formulas 1, 2 and 3 is 0.0 as a phosphorus element.
When dyeing a fiber made of polyester copolymerized with 5 to 4.0% by weight or a cloth made of the fiber, the pH of the dyeing liquor is maintained at 5.0 to 6.5, and an amine acetate salt is present in the dyeing liquor. A method for dyeing a phosphorus-containing polyester fiber or cloth, which comprises: