JPH05148415A - Polyester resin composition and polyester fiber - Google Patents

Abstract

(57) [Summary] [Structure] Cationic dye dyeable polyester resin obtained from a bifunctional carboxylic acid mainly comprising terephthalic acid or its ester-forming derivative, an alkylene glycol derivative or its ester-forming derivative and a specific sulfonate. In contrast, the following general formula (2) [In the formula, R ₃ and R ₄ represent an alkyl group, and the carbon number thereof is (R ₃
The number of carbon atoms of x × + the number of carbon atoms of R ₄ × m) is an integer of 12 to 54, q and m are integers of q + m = 1 to 4, p is 0 or 1, and Here, R ₁ and R ₂ represent H or an alkyl group having 4 or less carbon atoms. ] The compound represented by this is mix | blended. [Effect] By adding the compound represented by the general formula (2), the melt viscosity can be lowered without lowering the intrinsic viscosity of the cationic dye-dyeable polyester resin. By spinning such a cationic dye-dyeable polyester resin composition, a high-strength cationic dye-dyeable polyester fiber can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationic dyeable polyester resin composition and a polyester fiber. More specifically, a cationic dye-dyeable polyester resin composition having high strength and good dyeability, which is obtained by adding a melt viscosity reducing agent, and obtained by spinning the same

[0002]

2. Description of the Related Art Polyester is widely used because it has many excellent properties, but it has low dyeability and is difficult to dye with dyes other than disperse dyes. Various proposals have been made to improve this dyeability. As one of them, it has been conventionally known to copolymerize an isophthalic acid component containing a sulfonate with a polyester so that it can be dyed with a cationic dye (Japanese Patent Publication No. 34-104).
(See Japanese Patent Publication No. 97).

[0003]

However, in this method, the melt viscosity of the polymerization reaction product is remarkably increased due to the thickening effect of the isophthalic acid component containing the sulfonate, and the degree of polymerization is decreased due to the decrease in moldability. It is difficult to make it high, and it is difficult to obtain high-strength fiber.For example, it is not used alone for sportswear, paraglider wing fabric, sail for sailboats, suits, etc. It was

One of the methods for lowering the melt viscosity is to raise the melting temperature, but since the decomposition of the resin is promoted, the polymerization degree of the polymer is lowered, and a cationic dye having a high polymerization degree and high strength can be used. The purpose of obtaining dyed polyester cannot be achieved. Further, in order to solve these problems, the addition of a lubricant was considered, but for example, the addition of ethylene bis-stearic acid amide, stearic acid, stearyl alcohol, etc. as a lubricant in the resin reduces the melt viscosity, but at the same time the resin It has been found that it also reduces the degree of polymerization of.

[0005]

The inventors of the present invention have described the general formula
(2)

[0006]

[Chemical 4]

[Wherein, R ₃ and R ₄ represent an alkyl group, and the carbon number thereof is (carbon number of R ₃ × q + carbon number of R ₄ × m) = 12 to 54
, Q, m is an integer of q + m = 1 to 4, p is 0 or 1,

[0008]

[Chemical 5]

Here, R ₁ and R ₂ represent H or an alkyl group having 4 or less carbon atoms. ] When a compound represented by the following is added to a cationic dye-dyeable polyester resin, the melt viscosity is greatly reduced without significantly lowering the polymerization degree of the resin, and the moldability and spinnability are dramatically improved, Further, the inventors have found that a resin having a high degree of polymerization can be melt-spun, and a high-strength cationic dye-dyeable polyester fiber can be obtained, and the present invention has been completed.

That is, the present invention provides (a) a difunctional carboxylic acid mainly comprising terephthalic acid or an ester-forming derivative thereof, an alkylene glycol or an ester-forming derivative thereof, and a general formula (1)

[0011]

[Chemical 6]

(In the formula, A is an aromatic or aliphatic group, X ₁ is an ester-forming functional group, X ₂ is an ester-forming functional group or a hydrogen atom which is the same as or different from X _1, and M ^{n +} is an alkali metal or an alkaline earth group. (B) a polyester resin obtained from a sulfonate represented by a metal, onium, and n is 1 or 2.
General formula (2)

[0013]

[Chemical 7]

[Wherein, R ₃ and R ₄ represent an alkyl group, and the carbon number thereof is (carbon number of R ₃ × q + carbon number of R ₄ × m) = 12 to 54
, Q, m is an integer of q + m = 1 to 4, p is 0 or 1,

[0015]

[Chemical 8]

Here, R ₁ and R ₂ represent H or an alkyl group having 4 or less carbon atoms. ] A polyester resin composition comprising a compound represented by the following, and a polyester fiber obtained by spinning the same.

The polyester resin used in the present invention contains terephthalic acid as a main component and at least one glycol,
A polyester resin containing at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as a main glycol component is preferable.

Further, it may be a polyester resin in which a part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, or a part of the glycol component is replaced with the above glycol or another diol component other than the main component. It may be a replaced polyester resin.

Examples of the difunctional carboxylic acid other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid and p-oxybenzoic acid. , Adipic acid, sebacic acid,
Aromatic, aliphatic and alicyclic difunctional carboxylic acids such as 1,4-cyclohexanedicarboxylic acid can be mentioned.

Examples of the diol compound other than the above glycols include aromatic hexane, cyclohexyl-1,4-dimethanol, neopentyl glycol, bisphenol A, bisphenol S, aliphatic, alicyclic diol compounds and polyoxy compounds. Examples thereof include alkylene glycol.

The sulfonate component used as the copolymerization component is represented by the following general formula (1).

[0022]

[Chemical 9]

In the formula, A represents an aromatic group or an aliphatic group,
Of these, aromatic groups are preferred. X ₁ represents an ester-forming functional group, and as a specific example,

[0024]

[Chemical 10]

(However, R'is a lower alkyl group or a phenyl group, and m is an integer of 1 or more.) And the like. X ₂ represents an ester-forming functional group which is the same as or different from X ₁ , or a hydrogen atom, and among them, an ester-forming functional group is preferable. M ^{n +} is an alkali metal, alkaline earth metal or onium, and n is 1 or 2.

As the compound represented by the general formula (1), 5
-Sodium sulfoisophthalic acid, dimethyl 5-sodium sulfoisophthalate, bis (2-hydroxyethyl) 5-sodium sulfoisophthalate, bis (4-
Hydroxybutyl) 5-sodium sulfoisophthalate, 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid benzyltributylphosphonium Salt and the like. The sulfonates may be used alone or in combination of two or more. The ratio of copolymerizing the sulfonate with the polyester is preferably 0.1 to 10 mol%.

The intrinsic viscosity [η] of the polyester resin used in the present invention is 0.4 or more, preferably 0. 0 in a phenol / tetrachloroethane (60/40, weight ratio) solution at 25 ° C.
5 or more is good.

The compound added to the polyester in the present invention is represented by the following general formula (2).

[0029]

[Chemical 11]

[Wherein, R ₃ and R ₄ represent an alkyl group, and the carbon number thereof is (carbon number of R ₃ × q + carbon number of R ₄ × m) = 12 to 54
, Q, m is an integer of q + m = 1 to 4, p is 0 or 1,

[0031]

[Chemical 12]

Here, R ₁ and R ₂ represent H or an alkyl group having 4 or less carbon atoms. In the compound of formula (2) according to the present invention, the carbon number of R ₃ and R ₄ can be arbitrarily selected within the above range, but is preferably (carbon number of R ₃ × q + R ₄
The number of carbons x m) is preferably 16 to 36. (Number of carbon atoms in R ₃ × q +
If the number of carbon atoms in R ₄ × m) is less than 12, the molecular weight is too low to cause boiling at the melting temperature to generate bubbles, or smoke may contaminate the die. On the other hand, if it exceeds 54, the compatibility with the resin deteriorates and the effect is insufficient. R ₃ and R ₄ are specifically propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group,
Examples include octadecyl group and propylene tetramer residue.

The compound represented by the general formula (2) relating to the present invention can be easily obtained by a known method. For example, it can be obtained by reacting biphenyl, biphenyl ether, diphenyl sulfide or the like with an α-olefin having 9 to 18 carbon atoms in the presence of a catalyst such as aluminum chloride or boron trifluoride ethyl ether.

Specific examples of the compound represented by the general formula (2) according to the present invention are as follows.

[0035]

[Chemical 13]

The compound of the general formula (2) according to the present invention may be added to the cationic dye-dyeable polyester resin at any stage before melt spinning, at the time of resin production or at an appropriate step after production. Alternatively, it may be melt-mixed with resin pellets or molten resin at the time of spinning.

In order to exert the desired performance of the compound represented by the general formula (2) according to the present invention, 100 parts by weight of the cationic dye-dyeable polyester resin as a raw material (weight basis, the same applies hereinafter) is used. It is necessary to add 0.5 to 10 parts, preferably 1 to 5 parts, more preferably 2 to 5 parts of the compound. If the addition amount is less than 0.5, the effect can hardly be expected, and if it exceeds 10 parts, the physical properties of the resin are adversely affected.

Highly strong cationic dye-dyeable polyester fibers can be obtained from the cationic dye-dyeable polyester resin composition containing the compound of the general formula (2) according to the present invention. Cationic dye dyeable polyester copolymerized with sulfonate has a high melt viscosity, which causes an increase in discharge pressure and poor spinnability, so it is extremely difficult to use a high degree of polymerization polymer to improve strength. there were.

However, by adding the compound of the general formula (2) of the present invention to the cationizable dye-dyeable polyester resin, the spinning pressure and the yarn tension are lowered, and the spinning can be carried out smoothly.

The yarn discharged from the nozzle is once cooled and solidified. When a polyester resin is used for injection molding, promotion of crystallization during cooling is preferable for the purpose of improving moldability, but during melt spinning of the polyester resin, crystallization during cooling is not preferable. The melt viscosity reducing agent of the present invention does not cause crystallization of the resin during the cooling process from the spinning nozzle.

Further, the compound of the general formula (2) according to the present invention hardly decomposes even when exposed to a high temperature during melt spinning, and does not emit smoke or color, and has excellent heat resistance. .. Therefore, the molecular weight of the polymer does not decrease.

In the production of a cationic dye-dyeable polyester fiber having high strength, the compound represented by the general formula (2) is uniformly mixed with the cationic dye-dyeable polyester resin as a raw material as described above, and the mixture is melted. It is obtained by subjecting to spinning, cooling drawing, and heat treatment. The spun yarn is cooled and once wound up as an undrawn yarn and then preheated and drawn.
The heat treatment may be continued under tension, or the spun yarn may be taken up by a take-up roller without winding and then drawn and heat-treated at a heating roller.

Stretching and heat treatment can be carried out in the same manner as in ordinary cationic dye-dyeable polyester fibers. The preferred preheating temperature during stretching is 70 ° C to 90 ° C, and the preferred temperature for heat treatment is 150 ° C to 190 ° C. It is desirable that the stretched yarn elongation is 40% or less in order to obtain a high strength cationic dye-dyeable polyester fiber.

The polyester fiber of the present invention has excellent dyeability of a cationic dye, and its dyeing temperature can be appropriately changed depending on the polymer composition of the fiber, but is 85 ° C to 135 ° C.
Is preferable, and a range of 90 ° C to 130 ° C is more preferable.

[0045]

EFFECT OF THE INVENTION The compound represented by the general formula (2) according to the present invention makes it possible to lower the melt viscosity of the cationic dye-dyeable polyester resin without lowering the intrinsic viscosity, and further the degree of polymerization By facilitating the spinning of a cationic dye-dyeable polyester resin composition having a high viscosity, a high-strength cationic dye-dyeable polyester fiber can be realized.

[0046]

EXAMPLES The present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples.

Example 1 A compound shown in Table 1 was added to a cationic dye-dyeable polyethylene terephthalate resin having an intrinsic viscosity of 0.55 containing 2.5 mol% of 5-sodium sulfoisophthalic acid, and the mixture was melt-mixed by an extruder to obtain a resin. The strand was cooled with water and cut to obtain a sample. The melt viscosity of this resin composition was measured using a flow tester at 260 ° C, load 10 kgf, die diameter 1.0 mm, length 10
mm, and the plunger area was 1.0 cm ² . The sample after the flow tester measurement was dissolved in a phenol / tetrachloroethane (60/40, weight ratio) solution, and the intrinsic viscosity [η] at 25 ° C was measured. When [η] is the same as when no additive is added, it can be said that there is essentially no reduction in the degree of resin polymerization. The results are shown in Table 1.

[0048]

[Table 1]

Example 2 To 100 parts by weight of a cationic dye-dyeable polyethylene terephthalate resin having an intrinsic viscosity of 0.68 containing 2.5 mol% of 5-sodium sulfoisophthalic acid, 5 parts by weight of the compound of the present invention as a melt viscosity reducing agent was added and mixed. did. Insert the blend into an extruder-type melt spinning machine and spin at a spinning temperature of 280
It was discharged at a rate of 3 g / min from a spinning nozzle having a diameter of 0.5 mm at 0 ° C. The spun yarn was wound at a position of 2.5 m just below the nozzle at 1000 m / min. The undrawn yarn that has been wound up is drawn and heat-treated at a draw ratio that gives a final drawn yarn elongation of 30%, using a feed roller at 80 ° C and a plate heater at 180 ° C to obtain a drawn yarn. It was As a result, the nozzle pressure during spinning is
121 kgf / cm ² , the intrinsic viscosity of the undrawn yarn was 0.59, and the strength of the drawn yarn was 5.2 g / d.

Example 3 The same experiment as in Example 2 was conducted using the compound of the present invention as a melt viscosity reducing agent. As a result, the nozzle pressure during spinning was 124 kgf / cm ² , the intrinsic viscosity of the undrawn yarn was 0.59, and the strength of the drawn yarn was 5.1 g / d.

Example 4 The same experiment as in Example 2 was conducted using the compound of the present invention as a melt viscosity reducing agent. As a result, the nozzle pressure during spinning was 125 kgf / cm ² , the intrinsic viscosity of the undrawn yarn was 0.58, and the strength of the drawn yarn was 5.1 g / d.

Comparative Example 1 The same experiment as in Example 2 was conducted without adding the melt viscosity reducing agent of the present invention to a cationic dyeable polyethylene terephthalate having an intrinsic viscosity of 0.55 containing 2.5 mol of 5-sodium sulfoisophthalic acid. As a result, the nozzle pressure during spinning is
127 kgf / cm ² , the intrinsic viscosity of the undrawn yarn was 0.51, and the strength of the drawn yarn was 4.0 g / d.

Comparative Example 2 The same experiment as in Example 2 was conducted without adding a melt viscosity reducing agent to the cationic dye-dyeable polyethylene terephthalate having [η] = 0.68. As a result, the nozzle pressure during spinning was 17
It reached ² kgf / cm ^2, and yarn breakage was observed due to deterioration in spinnability.

Example 5 The same experiment as in Example 2 was conducted except that the addition amount of the compound of the present invention was 1.0.
It was made into parts by weight. As a result, the nozzle pressure during spinning was reduced to 159 kgf / cm ^2, and the intrinsic viscosity of the undrawn yarn was 0.58,
The yarn strength of the drawn yarn was 4.8 g / d.

Example 6 The same experiment as in Example 2 was conducted except that the addition amount of the compound of the present invention was 2.0.
It was made into parts by weight. As a result, the nozzle pressure during spinning was 142 kgf / cm ² , the intrinsic viscosity of the undrawn yarn was 0.59, and the strength of the drawn yarn was 4.8 g / d.

Example 7 The same experiment as in Example 2 was carried out with the addition amount of the compound of the present invention being 10 parts by weight. As a result, although the pressure in the nozzle during spinning was reduced to 109 kgf / cm ² , the intrinsic viscosity of the undrawn yarn was 0.56 and the strength of the drawn yarn was 4.5 g / d.

Comparative Example 3 5 parts by weight of a compound having the following structure as a melt viscosity reducing agent was added to 100 parts by weight of a cationic dye-dyeable polyethylene terephthalate resin having an intrinsic viscosity of 0.68 containing 2.5 mol% of 5-sodium sulfoisophthalic acid. The same experiment as in Example 2 was performed.

[0058]

[Chemical 14]

As a result, the nozzle pressure during spinning was 142 k.
It was observed that smoke was intense near gf / cm ² and the mouthpiece, and the undrawn yarn was slightly colored. The intrinsic viscosity of the undrawn yarn was 0.52, and the strength of the drawn yarn was 3.7 g / d, and the decrease in the molecular weight and the yarn strength was extremely large as compared with the melt viscosity reducing agent of the present invention.

Comparative Example 4 To 100 parts by weight of a cationic dye-dyeable polyethylene terephthalate resin having an intrinsic viscosity of 0.68 containing 2.5 mol% of 5-sodium sulfoisophthalic acid, 5 parts by weight of a compound having the following structure was added as a melt viscosity reducing agent. The same experiment as in Example 2 was performed.

[0061]

[Chemical 15]

As a result, the nozzle pressure during spinning was 166 k.
gf / cm ² , unstretched yarn was clouded and yarn breakage was observed. Almost no effect was observed as compared with the melt viscosity reducing agent of the present invention.

Example 8 The filament yarns obtained in Example 3 and Comparative Example 1 and ordinary polyethylene terephthalate (PET) filament yarns were dyed under the following conditions and the fastness of sublimation during storage was measured. Staining conditions Kayacryl Blue GSL-ED (Nippon Kayaku) 2% owf Rebenol TD-326 (Kao) 0.15 g / l Acetic acid 1.0 g / l Sodium sulfate 5.0 g / l Staining time 120 ℃ × 45 minutes Drying after soaping 120 ℃ × Sublimation fastness during storage for 1 minute was carried out under the following conditions by the method specified in JIS-L-0854. Treatment time 15 hours Storage humidity 90% RH Table 2 shows the results.

[0064]

[Table 2]

The addition of the melt viscosity reducing agent of the present invention did not affect the sharpness of dyeing and the fastness of sublimation during storage.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

However, by adding the compound of the general formula (2) of the present invention to the cationic dye-dyeable polyester resin, the spinning pressure and the yarn tension are lowered, and the spinning can be carried out smoothly.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

Production Example Dimethyl terephthalate 100 g, ethylene glycol 60
g, manganese acetate tetrahydrate 0.03 g (0.024 mol% with respect to dimethyl terephthalate) and cobalt acetate tetrahydrate 0.0
09 g (0.007 mol% with respect to dimethyl terephthalate) was charged into a transesterification reactor, and the temperature was raised from 140 ° C to 220 ° C over 3 hours in a nitrogen gas atmosphere while removing the generated methanol outside the system. Exchange reaction was performed. Subsequently, 2.5 mol% 5-sodium sulfoisophthalic acid was added to the product obtained in the form of a 20% heated ethylene glycol solution, and then the mixture was stirred at 220 ° C for 30 minutes, and then 56% of orthophosphoric acid was used as a stabilizer. 0.03 g of an aqueous solution (0.033 mol% based on dimethyl terephthalate) was added, and at the same time, distillation of excess ethylene glycol was started. After 10 minutes, 0.04 g of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added as a polycondensation catalyst. Content temperature is 240 ° C
When the temperature reached, the distillation of ethylene glycol was completed and the reaction product was transferred to a polymerization vessel. Then, while raising the temperature,
After reacting at atmospheric pressure until reaching 60 ℃, 1mmHg in 1 hour
And the internal temperature is raised to 280 ℃ at the same time.
The polycondensation reaction was carried out for 2.5 hours. This polymer was made into chips by a conventional method, embrittled with dry ice, and then pulverized.
The intrinsic viscosity of the obtained polymer was 0.55. Example 1 5-sodium sulfoisophthalic acid obtained in Preparation Example 2.
After adding 5 parts by weight of the compound shown in Table 1 to 100 parts by weight of a cationic dye-dyeable polyethylene terephthalate resin containing 5 mol% of an intrinsic viscosity of 0.55, the mixture was melt-mixed with an extruder, and the resulting strand was water-cooled and cut. It was used as a sample.
The melt viscosity of this resin composition was measured using a flow tester.
The measurement was carried out under conditions of ℃, load 10 kgf, die diameter 1.0 mm, length 10 mm and plunger area 1.0 cm ² . Sample after flow tester measurement is phenol / tetrachloroethane (60/40,
It was dissolved in a solution and the intrinsic viscosity [η] at 25 ° C. was measured. When [η] is the same as when no additive is added, it can be said that there is essentially no reduction in the degree of resin polymerization. The results are shown in Table 1.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

Example 3 The same experiment as in Example 2 was conducted using the compound of the present invention as a melt viscosity reducing agent. As a result, the nozzle pressure during spinning was 124 kgf / cm ² , the intrinsic viscosity of the undrawn yarn was 0.59, and the strength of the drawn yarn was 5.1 g / d.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

Example 4 The same experiment as in Example 2 was conducted using the compound of the present invention as a melt viscosity reducing agent. As a result, the nozzle pressure during spinning was 125 kgf / cm ² , the intrinsic viscosity of the undrawn yarn was 0.58, and the strength of the drawn yarn was 5.1 g / d.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location D01F 6/92 301 J 7199-3B // C08G 63/688 NNK 7211-4J

Claims (3)

[Claims] 1. A bifunctional carboxylic acid mainly comprising terephthalic acid or an ester-forming derivative thereof, an alkylene glycol or an ester-forming derivative thereof and a compound represented by the general formula (1): (In the formula, A is an aromatic or aliphatic group, X ₁ is an ester-forming functional group, X ₂ is an ester-forming functional group or a hydrogen atom which is the same as or different from X _1, and M ^{n +} is an alkali metal, an alkaline earth metal or an onium. , N is 1 or 2.), and a polyester resin obtained from a sulfonate represented by the following formula: (b) General formula (2) [In the formula, R ₃ and R ₄ represent an alkyl group, and the carbon number thereof is (R ₃
The number of carbons of x × the number of carbons of R ₄ × m) = an integer of 12 to 54, q, m is an integer of q + m = 1 to 4, p is 0 or 1, and Here, R ₁ and R ₂ represent H or an alkyl group having 4 or less carbon atoms. ] The polyester resin composition containing the compound represented by these. 2. The polyester resin composition according to claim 1, wherein the sulfonate is a sulfonated isophthalate. 3. A polyester fiber obtained by melt spinning the polyester resin composition according to claim 1.