JPH0718054B2 - Polyester fiber dyeable with modified basic dye and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyester fiber that can be dyed with a basic dye and a method for producing the same, and more specifically,
The present invention relates to a modified basic dye-dyeable polyester fiber which is remarkably improved in alkali hydrolysis resistance and is suitable for alkali reduction processing, and a method for producing the same.

[Conventional technology and its problems]

It has been well known that a basic dye-dyeable polyester fiber can be obtained by copolymerizing a metal sulfonate group-containing ester-forming component into the polyester component for the purpose of improving the dyeability and color developability of the polyester fiber. ing.

The basic dye-dyeable polyester fiber copolymerized with the metal sulfonate group-containing ester forming component has excellent dyeability,
Although it has a color-forming property, on the other hand, if the excellent alkaline hydrolyzability originally possessed by the homopolyester is significantly impaired, the drawbacks cannot be avoided.

By the way, the so-called alkali weight reduction processing, which creates a soft feel and drapable silk-like material by eluting the fiber surface with an alkaline solution by utilizing the moderate alkali hydrolysis property of homopolyester, is more It is now popular and popular to meet the needs of consumers who want something more luxurious and more diverse.

However, the current basic dye-dyeable polyester fibers, which have significantly higher alkali hydrolyzability than homopolyesters, are liable to (1) decrease in fineness or uneven fineness if they are subjected to alkali weight reduction processing.

(2) The strength tends to decrease.

(3) The fabric structure such as slips is likely to collapse.

There are obstacles, such as complicated management of alkali weight reduction processing operation,
In many cases, it is difficult or the alkali weight reduction processing itself cannot be performed.

Since the decrease in alkali hydrolysis resistance proceeds in proportion to the copolymerization ratio of the metal sulfonate group-containing ester-forming component, how is the effort to improve the alkali hydrolysis resistance of conventional basic dye-dyeable polyester fibers made? To reduce the amount of copolymerization of the metal sulfonate group-containing ester forming component and to improve the dyeing level in that state.

One of the methods is to polymerize another third component. (JP-A-51-136922, JP-B-57-32139, etc.) In this method, the fiber structure is made looser by the introduction of the third component to improve the diffusibility of the basic dye into the fiber. The present invention aims to maximize the effective use of dyeability with a small amount of a metal sulfonate group-containing ester forming component, and certainly succeeded in reducing the metal sulfonate group-containing ester forming component and improving the dyeing level. However, the looseness of the fiber structure causes a new decrease in alkali hydrolysis resistance, in addition to the influence exerted by the metal sulfonate group-containing ester forming component, and reduces the metal sulfonate group-containing ester forming component. However, the decrease in alkali hydrolysis resistance was still large.

As another method, a method of improving the dyeing level with a small amount of the metal sulfonate group-containing ester forming component by spinning a polyester copolymerized with the metal sulfonate group-containing ester forming component at a winding speed of 5000 m / min or more is proposed. (Japanese Patent Publication No. 53-139820). However, since the alkali hydrolysis resistance is gradually reduced by high-speed spinning, it is possible to reduce the metal sulfonate group-containing ester forming component, but the alkali hydrolysis resistance cannot be improved and is rather deteriorated. There is even a tendency. Moreover, it has been found that high-speed spinning causes new problems when fluffing and yarn breakage increase during spinning.

[Means for solving problems]

The present invention has been achieved as a result of diligent efforts to solve the above-mentioned drawbacks. That is, the present invention, when producing a basic dye-dyeable polyester fiber by polymerizing a metal sulfonate group-containing ester-forming component into a polyester mainly composed of ethylene terephthalate units, by further polymerizing a specific copolymerization component, A basic dye-dyed easily dyeable modified polyester fiber which improves the low alkaline hydrolysis performance of the basic dye-dyed polyester fiber and is capable of alkali reduction processing like ordinary homopolyester, and a method for producing the same Is to provide.

In the basic dye-dyeable polyester fiber constituting the present invention, a metal sulfonate group-containing ester-forming component and a 1,2-bis (4-carbophenooxy) shietane component are copolymerized with a polyester mainly containing ethylene terephthalate units. It is necessary.

That is, the metal sulfonate group-containing ester-forming component is an essential component for dyeing with a basic dye because it has a dyeing seat that binds to the basic dye, and the component is specifically, for example, 5-sodium. Dicarboxylic acids such as sulfoisophthalic acid, potassium sulfoterephthalic acid, sodium sulfonaphthalenedicarboxylic acid, sodium sulfophenyldicarboxylic acid and their alkyl esters, oxycarboxylic acids such as sodium sulfobenzoic acid and their alkyl esters, and dihydroethoxy. Dihydroxy compounds such as sodium benzenesulfonate are preferred, and 5-sodium sulfoisophthalic acid is particularly preferred.

Further, 1,2-bis (4-carbophenooxy) ethane is a main part of the constituent features of the present invention and is indispensable for improving alkali hydrolyzability. Usually, when a third component is copolymerized with a homopolyester, the structure becomes loose and alkali hydrolyzability progresses, but surprisingly, 1,2-bis (4-carbophenooxy) ethane is polymerized. It has the function of suppressing the alkali hydrolyzability, and it is the first time that the alkali hydrolyzability is suppressed by copolymerizing the third component with the polyester obtained by polymerizing the metal sulfonate group-containing ester-forming component. .

The copolymerization mol% of the metal sulfonate group-containing ester forming component is preferably 0.5 to 4.0. Mol% of the copolymer,
If it is less than 0.5, the number of basic dye dyeing seats is small, so it will be dyed only in a light color, and if it exceeds 4.0, it will be due to the increase in the melt viscosity at the time of polymerization that the metal sulfonate group-containing ester-forming component originally has. Deterioration of the degree of polymerization is reached, and adverse effects such as an increase in spinneret packing pressure during spinning and yarn breakage become noticeable.

Further, the copolymerization mol% of the 1,2-bis (4-carbophenooxy) ethane component is preferably 2.0 to 20.0. When the mol% of the copolymer is less than 20, the effect of improving the alkali hydrolyzability cannot be expected, and when it exceeds 20.0, other physical properties such as melting point are largely deteriorated, which is not preferable in practice.

The mixing ratio of these two components can be freely selected within their respective ranges, but it is desirable to carry out the polymerization by appropriately considering the balance of dyeability, alkali hydrolyzability, mechanical and thermal properties, and the like.

A known method can be adopted as a method for polymerizing the copolymerization component constituting the present invention.

That is, the dicarboxylic acid component is terephthalic acid as an acid,
It may be reacted directly with ethylene glycol or the like, or may be subjected to transesterification with ethylene glycol as an alkyl ester component such as dimethyl ester and then polycondensed.

The glycol component can be used similarly to ethylene glycol.

The oxycarboxylic acid component can also be polymerized in the same manner as the dicarboxylic acid.

The polymer obtained by polymerization by these known methods can be spun by any known spinning method to form a fiber, which is the object of the present invention.

Generally, the following three methods can be roughly divided into (1) spinning at a winding speed of 1000 to 1500 m / min, and the unstretched yarn is stretched 3 to 4 times as heat treatment. (2) The so-called PO is spun at a winding speed of 4000 m / min or less.
Y is set, and the POY is drawn and false twisted at 1.05 to 1.5 times.

(3) High-speed spinning is performed at a winding speed of 5000 m / min or more.

Among them, the method (3) by high-speed spinning is a preferable method because it can improve the productivity and can reduce the cost by omitting the drawing step and can also expect the effect of improving the dyeability.

However, in general, spinning a polyester copolymerized with a metal sulfonate group-containing ester-forming component at 5000 m / min or more often causes fluffing or yarn breakage, which makes winding difficult. It was not suitable as a method for producing polyester fibers. However, surprisingly, the polyester of the present invention can be produced with remarkably little generation of fluff and yarn breakage even when wound up and spun at 5000 m / min or more, and can be produced similarly to the homopolyester.

〔effect〕

The modified basic dye-dyeable polyester fiber of the present invention has a high alkali hydrolysis resistance which cannot be obtained by the conventional basic dye-dyeable polyester fiber, and therefore, the conventional basic dye. It is effective to make it possible to easily carry out the alkali weight reduction processing which was difficult with dyeable polyester fibers.

In addition, as another effect, when the fiber is produced by spinning at a winding speed of 5000 m / min or more, the problem of fluff and yarn breakage, which has been frequently encountered in the production of this type of fiber, is solved, and productivity is improved. Can be improved.

〔Example〕

 The present invention will be specifically described below with reference to examples.

The evaluation methods of various characteristic values used in the examples of the present invention are as follows.

(Strength, Elongation) Shimadzu Corporation, using Autograph DSC100 type tensile tester,
The initial length is 20 cm and the pulling speed is 20 cm / min.

(Boiling water shrinkage rate) Let L be the sample length under a load of 0.1 g / d, remove the load,
After treating in boiling water for 30 minutes, the length measured under the same load is defined as L, and the boiling water shrinkage rate (abbreviated as BWS) is calculated from the following equation.
Define and ask.

(Basic dye exhaustion rate) Basic dye Maxilon Blue 5G (Chiba Geigy) Preparation liquid: Sodium acetate 0.5g / L Anhydrous sodium sulfate 4.0g / L Acidity pH = 4.5 Bath ratio 1:50 Dye concentration = 5% owf Temperature 95 ℃ Dissolve the dye in the adjustment liquid, after dyeing under the above conditions,
The residual liquid was diluted with the adjustment liquid, and the absorbance (U) was measured at a wavelength λ = 655 mμ by a Shimadzu spectrophotometer UV-200 using a 1 cm corex cell. The basic dye exhaustion rate (simply abbreviated as exhaustion rate) is calculated from (Uo).

(Melting point) Perkin Elma Differential Scanning Calorimete
Using r-2 type, sample 7 mg, heating rate 20 ° C / min,
The melting point is the apex of the endothermic peak of the chart obtained by measurement while performing N ₂ substitution.

(Alkali weight loss rate) After the sample (thread) is knitted on a knitting machine, a surfactant (score roll) is used.
250 Kao Atlas Co., Ltd.) is dissolved in distilled water at a rate of 2 g / L, and is scoured for 30 minutes at a bath ratio of 1: 200 and a bath temperature of 60 to 70 ° C. to remove the oil.

After scouring, drain the water well and dry for 24 hours in a thermostatic chamber maintained at a temperature of 23 ° C and a humidity of 65%.

Measurement Pre-processed sample is weighed accurately about 5g (Wo), NaOH 5% aqueous solution, alkali hydrolysis of the sample for 15 minutes in boiling state,
Then, it is washed well with water, dehydrated, dried under the above conditions, the weight (W) after weight loss is accurately measured, and the alkali weight loss rate is defined and obtained by the following equation.

Example 1 3.36 parts by weight of 5-sodium sulfoisophthalic acid (2.2 mol%), 1,2-bis (4-carbophenooxy) ethane 7.7
8 parts by weight (5 mol%), dimethyl terephthalate 92.8 parts by weight, ethylene glycol 70.0 parts by weight, manganese acetate 0.04
7 parts by weight and 0.06 parts by weight of lithium acetate were charged into an autoclave equipped with a rectification column, and while heating the methanol to be purified by distillation, the mixture was heated at 180 to 240 ° C. for 2 hours with stirring to obtain 97% or more of the theoretical reaction methanol amount. After distilling off, the reaction product was transferred to a depressurizing autoclave, and 0.04 part by weight of antimony oxide and 0.03 part by weight of phosphorous acid were added, and the temperature was raised to 265 ° C and the degree of vacuum was gradually raised to a degree of vacuum of 0.5 mm / Hg or less. And continue the polymerization for 2 hours while raising the temperature to 285 ° C, melting point 238 ° C,
A copolymerizable polyethylene terephthalate dyeable with a basic dye having an intrinsic viscosity of 0.59 was obtained.

The copolymerized polyethylene terephthalate was crushed into pellets and dried under reduced pressure at 130 ° C. for 20 hours to adjust the water content.

The copolymerized polyethylene terephthalate pellets were extruded at a melting temperature of 295 ° C through a spinneret equipped with 24 holes with a spinneret diameter of 0.23 mm at a discharge rate of 37.4 g / min, and 40 cm immediately below the spinneret.
After passing through a heating cylinder maintained at a temperature of 210 ℃, attach a nozzle guide for refueling located 130 cm below the spinneret and focus it to 7000
It was wound as a fiber of 50 denier / 24 filament at a winding speed of m / min.

The evaluation results of strength, elongation, boiling water shrinkage (BWS), exhaustion rate, alkali weight loss rate, and spinning stability are shown in the table.

As you can see from the table, it is the alkali weight loss rate, or 1,2-
It can be seen that the bis (4-carbophenooxy) ethane is not copolymerized and is greatly improved as compared with the basic dye-dyeable polyester. However, the fiber is 7,000 m / mi
Despite being manufactured at a high winding speed of n,
The result shows that the occurrence of yarn breakage and fluff during spinning is less than that of the conventional uncopolymerized product.

Example 2 The copolymerized polyethylene terephthalate of Example 1 was extruded in the same manner as in Example 1 at a spinning temperature of 295 ° C. and a discharge rate of 16.0 g, and was wound at a winding speed of 800 m / min through a heat retention / cooling unit. Furthermore, the unstretched fiber is immediately stretched at a stretch ratio of 3.617.
The film was stretched twice under the conditions of a temperature of 70 ° C.

The physical properties of the obtained fiber are also shown. As can be seen from the table, the value of the alkali weight loss rate is greatly improved.

Comparative Examples 1 and 2 In the same manner as in Example 1, copolymerized polyethylene terephthalate was polymerized without copolymerizing 1,2-bis (4-carbophenooxy) ethane, and the same method as in Examples 1 and 2 Spun in. The results are shown in Table 1. As can be seen from Table 1, the value of the alkali weight loss rate is large, and in high-speed spinning,
I knew that thread breakage, fluffing, and productivity were poor.

Claims (3)

[Claims] 1. A metal sulfonate group-containing ester-forming component of 0.5 to 4.0 mol% and 1,2-bis (4-) of 2.0 to 20.0 mol%.
A modified basic dye-dyeable polyester fiber mainly comprising ethylene terephthalate units, characterized in that a carbophenooxy) ethane component is copolymerized. 2. The modified basic dyeable polyester fiber according to claim 1, wherein the metal sulfonate group-containing ester forming component is 5-sodium sulfoisophthalic acid. 3. 0.5 to 4.0 mol% of a metal sulfonate group-containing ester-forming component and 2.0 to 20.0 mol% of 1,2-bis (4-)
Manufacture of polyester fiber dyeable with modified basic dyes, characterized by spinning a polyester mainly composed of ethylene terephthalate units obtained by copolymerizing a carbophenoxy) ethane component at a winding speed of 5000 m / min or more. Method.