JP2804977B2 - Hygroscopic polyester resin and fiber consisting thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin and a polyester fiber using the same. More specifically, a polyester resin having an excellent hygroscopicity and antistatic property containing a sulfamic acid (salt) group in a molecule, and a water absorbing property, antistatic property, cationic dye dyeing property and the like obtained by spinning the polyester resin. The present invention relates to a polyester fiber which is excellent in water resistance.

[0002]

2. Description of the Related Art Polyester has many excellent properties and is widely used for various molding materials and fibers. However, since it is inherently hydrophobic, it lacks moisture absorption and antistatic properties. In particular, the field of use is extremely limited for use in textiles. For this reason, various proposals have conventionally been made to impart hygroscopicity and antistatic properties to polyester fibers, for example, by adding a hydrophilic compound such as polyoxyalkylene glycol to polyester forming a fiber to react or react. Mixing method (JP-A-47-29486)
JP-A-59-47480, etc.) have been proposed. In addition, polyester fiber has low dyeability,
In particular, it is difficult to dye a dye other than a disperse dye. Various proposals have been made to improve the dyeability. Part 1
For example, a method is known in which an isophthalic acid component containing a sulfonic acid salt is copolymerized with a polyester to enable dyeing with a cationic dye (for example, Japanese Patent Publication No.
No. 10497).

[0003]

However, regarding the provision of hygroscopicity, the hygroscopicity obtained by the addition of a hydrophilic compound proposed so far is not sufficient, and
When these hydrophilic compounds are added in a large amount to impart sufficient hygroscopicity, physical properties such as fiber strength are reduced, and the excellent properties inherent in polyester fibers are sacrificed. Regarding the improvement of dyeability, the method of copolymerizing the isophthalic acid component containing a sulfonate into a polyester significantly increases the viscosity during polymerization due to the thickening action of the isophthalic acid component containing a sulfonate. However, it was difficult to increase the degree of polymerization, and it was difficult to obtain fibers having high strength. Further, in order to reduce the viscosity, the addition of a lubricant was considered, for example, adding ethylene bisstearic acid amide, stearic acid, stearyl alcohol, etc. as a lubricant lowers the viscosity, but at the same time lowers the polymerization degree of the resin. There was a problem.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on polyester fibers having high hygroscopicity and high-strength cationic dye-dyeable polyester fibers while maintaining the excellent properties inherent in polyesters. The invention has been reached. That is, the present invention is obtained by reacting a bifunctional carboxylic acid or its ester-forming derivative (A), an alkylene glycol (B), and a sulfamic acid (salt) group-containing compound (C) represented by the following general formula (1). Moisture-absorbing polyester resin; [In the formula, X ¹ and X ² each independently represent an organic group having one hydroxyl group, an organic group having one carboxyl group or an ester-forming derivative thereof, or a hydrogen atom (provided that X ¹ and X ² Is not a hydrogen atom.), M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a tertiary amine or a quaternary ammonium, and a represents an ionic value of M. And a polyester fiber obtained by melt spinning the resin and a polyester fiber dyed with a cationic dye.

[0005]

Specific examples of X ¹ and X ² in sulfamate represented by the above general formula (1) (salt) group-containing compound (C) DETAILED DESCRIPTION OF THE INVENTION At least one of X ¹ or X ² is, Having an alkyl group having a hydroxyl group, an aryl group having a hydroxyl group, a group in which an alkylene oxide (ethylene oxide, propylene oxide, butylene oxaide, etc.) is (co) added to these hydroxyl groups, a carboxyl group or a lower alkyl ester thereof. And an aryl group. Of these, preferred are diols containing a sulfamic acid (salt) group in which X ¹ and X ² are hydroxyl group-containing organic groups. Also, M
Specific examples of a hydrogen atom, an alkali metal (such as lithium, sodium, and potassium), an alkaline earth metal (such as magnesium and calcium), a tertiary amine (such as triethylamine), ammonium, and a quaternary ammonium (tetramethylammonium) Etc.).
Particularly preferred as M is an alkali metal.

Examples of the above-mentioned sulfamic acid (salt) group-containing diols include 2-sulfamino-1,3-propanediol, 3-sulfamino-1,2-propanediol, and 2-sulfamino-2-methyl-1,3. Aliphatic compounds having a hydroxyl group such as propanediol, N, N-bis (hydroxyethyl) sulfamic acid or alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts of these compounds;
Aromatic compounds containing hydroxyl groups such as N, N-bis (p-hydroxyphenyl) sulfamic acid or alkylene oxide adducts of these compounds;
Examples thereof include alicyclic compounds containing a hydroxy group such as N-bis (4-hydroxycyclohexyl) sulfamic acid, and alkylene oxide adducts of these compounds.

Of these, particularly preferred are those represented by the following general formula (2): [Wherein, R ¹ and R ² each independently have 2 to 4 carbon atoms.
And Z is sodium or potassium, and m and n each independently represent an integer of 1 to 100. ]
It is a compound shown by these. In the above formula (2), m and n are each independently usually an integer of 1 to 100,
Preferably, it is an integer such that the sum of m and n is 2 to 100. If m or n exceeds 100, the sulfamic acid (salt) group concentration in the sulfamic acid (salt) group-containing compound will be low, and sufficient hygroscopicity or cationic dye dyeability will be maintained while maintaining the inherent properties of the polyester resin. Is difficult to provide.

As a method of synthesizing the sulfamic acid (salt) group-containing diol, for example, an amino group-containing diol is reacted with a pyridine-sulfur trioxide complex in an aqueous alkali solution at a temperature of 0 to 40 ° C. ethanol,
An example is a method of obtaining the target product by refining with a method such as recrystallization with acetone.

Specific examples of the polycarboxylic acids containing sulfamic acid (salt) include aromatic dicarboxylic acids containing a sulfoamino group such as 2-sulfoaminoterephthalic acid, 3-sulfoaminophthalic acid and 5-sulfoaminoisophthalic acid. Acids, 2-hydroxy-4-sulfaminoaminobenzoic acid, 2-hydroxyethyl-4-sulfaminoaminobenzoic acid, 3-hydroxy-2-sulfaminoaminobenzoic acid, 3-
Examples thereof include aromatic oxysulfoaminobenzoic acids such as hydroxyethyl-2-sulfoaminobenzoic acid and salts thereof.

As a method for synthesizing the sulfamic acid (salt) group-containing polycarboxylic acid, for example, an amino group-containing polycarboxylic acid is reacted with a pyridine-sulfur trioxide complex at a temperature of 0 to 40 ° C. in an aqueous alkali solution. Thereafter, the reaction product is purified by a method such as recrystallization with ethanol, acetone, or the like to obtain the desired product.

Examples of the ester-forming bifunctional carboxylic acid or its ester-forming derivative (A) include terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalic acid, diphenyldicarboxylic acid, and naphthalidinedicarboxylic acid. Aromatic dicarboxylic acid or its ester-forming derivative; aromatic oxycarboxylic acid such as diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-hydroxyethoxybenzoic acid, p-hydroxybenzoic acid or its ester-forming derivative , Succinic acid,
Adipic acid, azelaic acid, sebacic acid, dimer acid,
Examples thereof include aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and dodecanedicarboxylic acid, and ester-forming derivatives thereof, and mixtures of two or more of these. If necessary, a trivalent or higher carboxylic acid such as trimellitic acid, trimesic acid or hydromellitic acid or an ester-forming derivative thereof may be used in combination. The term "ester-forming derivative" as used herein means an acid chloride of a corresponding carboxylic acid, an ester of a lower alcohol, or the like.

Examples of the alkylene glycol (B) include ethylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, , 8-octamethylene glycol, 1,1
Alkylene glycols such as 0-decanediol; cyclohexanediol, cyclohexanedimethanol, bis (hydroxycyclohexyl) methane, xylylene glycol, bis (hydroxyethyl) benzene, 1,4
-Bis (2-hydroxyethoxy) benzene, 4,4 '
Low-molecular-weight diols having a cyclic group such as -bis (2-hydroxyethoxy) -diphenylpropane (ethylene oxide adduct of bisphenol A); and mixtures of two or more of these. If necessary, trihydric polyhydric alcohols such as trimethylolethane, trimethylolpropane, glycerin and pentaerythritol may be used in combination.

As the method of the esterification reaction, any method can be used. For example, the above-mentioned (A), (B) and (C) can be polycondensed by a known method, if necessary, in the presence of an esterification catalyst. A method for causing the reaction is mentioned.

The content of the sulfamic acid (salt) group in the polyester resin of the present invention is 10 ⁶
Usually 20 to 2000 equivalents per g, preferably 200 to
It is 2,000 equivalents, more preferably 200-1200 equivalents. If it is less than 20 equivalents, the hygroscopicity and antistatic properties will be insufficient, and if it exceeds 2000 equivalents, the resin properties will be reduced.
When the primary purpose is cationic dye dyeability, it is usually 2
0 to 850 equivalents.

The intrinsic viscosity [η] of the polyester resin of the present invention in a phenol / tetrachloroethane (60/40 weight ratio) solution at 25 ° C. is usually 0.4 or more, preferably 0.5 or more. When [η] is less than 0.4, the strength of the fiber becomes insufficient.

In producing the hygroscopic polyester fiber of the present invention, the hygroscopic polyester resin obtained by copolymerizing a sulfamic acid (salt) group-containing compound is spun in a molten state, cooled, drawn and heat-treated. . The spun yarn may be preheated after being wound once as a drawn yarn after cooling, and then heat-treated under tension, or may be taken up by a take-up roller without winding the spun yarn, and then drawn on a heating roller. , May be heat-treated.

The drawing and heat treatment can be carried out in the same manner as for ordinary polyester fibers. The preferred preheating temperature during stretching is 70 ° C to 90 ° C, and the preferred temperature for heat treatment is 1 ° C.
50 ° C to 190 ° C. In order to obtain a high-strength polyester fiber, the elongation of the drawn yarn is desirably 40% or less.

The polyester fiber of the present invention has excellent cationic dyeability. The dyeing temperature can be suitably changed depending on the polymer composition constituting the fiber, but is preferably in the range of 85 to 135 ° C, more preferably 90 to 130 ° C.

The dyeability and the fastness of sublimation during storage of polyester fibers made with the cationic dye of the present invention are extremely good.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The method for measuring the characteristics shown in the examples is as follows. [Hygroscopicity] After the prepared drawn yarn was absolutely dried at 105 ° C for 2 hours,
The humidity was controlled in an atmosphere of 20 ° C. × 90% RH for 24 hours, and the moisture absorption was determined by the following equation. Moisture absorption = (weight of stretched yarn after humidity control−weight of absolutely dry stretched yarn) / weight of absolutely dry stretched yarn × 100 [Strength] The tensile strength of the stretched yarn was measured using a tensile tester. [Dyeing property] The obtained drawn yarn was subjected to 5.0 owf of Sebron Blue B (manufactured by DuPont, cationic dye), 0.2 g / l of acetic acid and sodium acetate each, a bath ratio of 1: 100, and a boiling point of 90 at normal pressure. After staining for minutes, the dyeing rate was calculated from the absorbance of the staining solution before and after staining.

Comparative Example 1 166 g (1 mol) of terephthalic acid and 74.4 g of ethylene glycol were placed in an autoclave equipped with a condenser and a stirrer.
(1.2 mol) and lithium acetate dihydrate 0.01 g
And the inside of the reactor was replaced with nitrogen gas, and then 3 kg / cm ²
The nitrogen gas of G was sealed, the temperature was raised to 240 ° C. with stirring, and the reaction was continued at 240 ° C. until water distillation stopped.
After cooling to 180 ° C., 0.5 g of lithium acetate dihydrate and manganese acetate tetrahydrate 0.02 from the sampling port.
g, the temperature was raised to 270 ° C., and the pressure was gradually reduced.
The reaction was completed at a temperature of not more than mmHg for 3 hours to obtain a polyethylene terephthalate resin for comparison with an intrinsic viscosity of 0.68. The obtained polyethylene terephthalate resin was put into an extruder-type melt spinning machine, and the spinning temperature was adjusted to 28.
At 0 ° C., the mixture was discharged from a spinning nozzle having a diameter of 0.5 mm at a rate of about 3 g / min. The spun yarn was wound at a position of 2.5 m immediately below the nozzle at 1000 m / min. The drawn undrawn yarn is drawn and heat-treated using a supply roller at 80 ° C. and a plate heater at 180 ° C. at a draw ratio at which the elongation of the finally obtained drawn yarn is 30%, to obtain a drawn yarn. Was. Table 1 shows the strength and hygroscopicity measurement results of the obtained drawn yarn.

Example 1 A part of ethylene glycol in Comparative Example 1 was N, N-
The same operation as in Comparative Example 1 was performed in place of di (2-hydroxyethyl) sulfamic acid sodium salt, and sodium sulfamate-based salt was added in an amount of 4 per 10 ⁶ g of the polyester resin.
A polyester resin and a drawn yarn of the present invention having an intrinsic viscosity of 0.68 and containing 45 equivalents were obtained. Table 1 shows the strength and hygroscopicity measurement results of the obtained drawn yarn.

Example 2 Comparative Example 1 A part of ethylene glycol was replaced with N, N-di (2-
The same operation as in Comparative Example 1 was carried out except that the ethylene oxide 10 mol adduct of (hydroxyethyl) sulfamic acid sodium salt was used, and an intrinsic viscosity of 0.68 in which 777 equivalents of sodium sulfamate were contained per 10 ⁶ g of the polyester resin. The polyester resin and the drawn yarn of the invention were obtained. Table 1 shows the strength and hygroscopicity measurement results of the obtained drawn yarn.

Example 3 A part of the ethylene glycol of Comparative Example 1 was replaced with N, N-di (2
- hydroxyethyl) sodium sulfamate instead of ethylene oxide 60 mol adduct A similar experiment was carried out as in Comparative Example 1, the intrinsic viscosity 0.68 with sodium sulfamate base was contained 204 per polyester resin 10 ⁶ g equivalents A polyester resin and a drawn yarn of the present invention were obtained. Table 1 shows the strength and hygroscopicity of the obtained drawn yarn.

Comparative Example 2 The same operation as in Comparative Example 1 was carried out except that part of the terephthalic acid in Comparative Example 1 was replaced with 5-sodium sulfoisophthalic acid, and a sodium sulfonate group was co-containing 118 equivalents per 10 ⁶ g of the polyester resin. A comparative polyester resin and a drawn yarn having an intrinsic viscosity of 0.35 were obtained. Table 1 shows the strength and dyeing ratio of the obtained drawn yarn.

Example 4 The same operation as in Comparative Example 1 was carried out except that part of the ethylene glycol of Comparative Example 1 was changed to 2-potassium sulfoamino-1,3-propanediol, and potassium sulfamate was converted to a polyester resin 10 ⁶ A polyester resin of the present invention and a drawn yarn having an intrinsic viscosity of 0.68 and 117 equivalents per g were obtained. Table 1 shows the strength and dyeing rate of the obtained drawn yarn.
Shown in

[0027] Example 5 a portion of terephthalic acid of Comparative Example 1 The same procedure as in Comparative Example 1 instead of the sodium 2-sulfo-amino terephthalic acid, 117 per polyester resin 10 ⁶ g of sodium sulfamate base Toryotomo Polymerized intrinsic viscosity 0.6
In this way, 8 polyester resins and drawn yarns of the present invention were obtained. Table 1 shows the strength and dyeing ratio of the obtained drawn yarn.

Example 6 The same operation as in Comparative Example 1 was carried out except that a part of the ethylene glycol of Comparative Example 1 was replaced with 2-sodium sulfoamino-1,3-propanediol, and a sodium resin sulfamate was used as a polyester resin 10 ⁶ A polyester resin and a drawn yarn of the present invention having an intrinsic viscosity of 0.68 and containing 846 equivalents per gram were obtained. Table 1 shows the strength and dyeing ratio of the obtained drawn yarn.

Example 7 The same operation as in Comparative Example 1 was carried out except that part of the ethylene glycol of Comparative Example 1 was changed to 2-sodium sulfoamino-1,3-propanediol, and a sodium sulfamate base was converted to a polyester resin 10 ⁶ A polyester resin and a drawn yarn of the present invention having an intrinsic viscosity of 0.68 and containing 24 equivalents per gram were obtained. Table 1 shows the strength and dyeing ratio of the obtained drawn yarn.

[0030]

Table 1-------------------------Strength-g / d Moisture absorption% Dyeing%- −−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative example 1 5.3 1 −−−−−−−−−−−−−−−−−−−−−−− Example 1 5.3 11 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 2 5.2 13 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 3 5.1 18 −−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative example 2 4.0 −−95 −−−−−−−−−−−−−−−−−−− Example 4 5.3-99------------------------------------------------------------------------------------------------------------- Example 5 5.2 −−98 −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 6 4.9 −−99 −−−−−−−−−− Example 7 5.3 --- 99 ------------------------------------- −−−−−−−−−

[0031]

The polyester fiber obtained by using the hygroscopic polyester resin of the present invention can have a permanent hygroscopic property without impairing the original properties of the polyester fiber such as the fiber strength. . Further, since the increase in viscosity during polymerization is small, it is possible to produce a resin having a high degree of polymerization, and it is possible to obtain a polyester fiber having high strength and cationic dyeability.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI D06P 5/22 D06P 5/22 C (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 63/00-63/91 D01F 6 / 84 306 D01F 6/86 305

Claims (5)

(57) [Claims] 1. A method comprising reacting a bifunctional carboxylic acid or an ester-forming derivative thereof (A), an alkylene glycol (B), and a sulfamic acid (salt) group-containing compound (C) represented by the following general formula (1). Hygroscopic polyester resin. [In the formula, X ¹ and X ² each independently represent an organic group having one hydroxyl group, an organic group having one carboxyl group or an ester-forming derivative thereof, or a hydrogen atom (provided that X ¹ and X ² Is not a hydrogen atom.), M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a tertiary amine or a quaternary ammonium, and a represents an ionic value of M. ] 2. The polyester resin according to claim 1, wherein (C) is a compound represented by the following general formula (2). [Wherein, R ¹ and R ² each independently have 2 to 4 carbon atoms.
And Z is sodium or potassium, and m and n each independently represent an integer of 1 to 100. ] 3. The polyester resin according to claim 1, wherein the content of the sulfamic acid (salt) group in the resin is 20 to 2,000 equivalents per 10 ⁶ g of the resin. 4. A hygroscopic polyester fiber obtained by melt-spinning a polyester resin comprising the resin according to claim 1. 5. A polyester fiber obtained by dyeing a fiber comprising the resin according to claim 1 with a cationic dye.