DE2502550A1 - CARRIER-FREE BASIC POINTABLE POLYESTER FIBERS AND FIBERS - Google Patents

Description

Bayer Aktiengesellschaft 2502550

Central area of patents, trademarks and licenses

509 Leverkusen. Bayerwerk

Sdt / Bre

2 JAN. 1975

Carrier-free, alkaline dyeable polyester threads and fibers

The invention relates to carrier-free "base-dyeable polyester fibers and threads.

The manufacture of threads and fibers from linear thread-forming Polyesters have been known for a long time. Here, dicarboxylic acids are reacted with diols to form high molecular weight linear polyesters and then spun them. Terephthalic acid, isophthalic acid and hexahydroterephthalic acid are examples of dicarboxylic acids in question. The glycols are ethylene glycol, 1,4-butanediol, 1,3-propanediol or 1,4-bis- (hydro3cy-methyl) -cyclohexane mentioned by way of example. The best-known representative of this polyester class is polyethylene terephthalate.

The threads produced from such polyesters by the melt-spinning process are usually bundled, drawn in hot water or another medium, fixed in hot air, crimped and cut, if they are not fed to further use as such. The fibers produced in this way normally have a strength of 2.5 4.5 p / dtex, an elongation of 20-50% and a boiling shrinkage of 0-3%.

Textiles with excellent Wear properties such as low susceptibility to creasing, low water absorption and therefore easy drying or high strength and produce good abrasion resistance.

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ORIGINAL INSPECTED

Since it is preferred, for reasons of cost, no spun-dyed threads To process for the textiles, the process described above must be followed by a dyeing process. This often occurs Difficulties arise because textiles made from polyester fibers, especially those made from polyesters based on terephthalic acid and ethylene glycol and / or 1,4-bis (hydroxymethyl) cyclohexane are produced, stain poorly in a normal dyeing process permit. The reason is to be found in the fact that no reactive groups are present in the polymer chain and therefore there is hardly any affinity for most dyes.

Only with the disperse dyes did a group of dyes become found that dissolves in the fiber material.

However, attempts have also been made to incorporate reactive groups into the polymer chain, such as 5-sulfoisophthalic acid to thus having the option of using basic dyes in addition to the disperse dyes. As a result of this Developments can be said that the absorption rate both the dispersion and the acidic or, as in the case of installation of 5-sulfoisophthalic acid, the basic dyes too was low so that only light or medium tones were obtained. Special dyeing processes were required to obtain darker shades to be developed.

For polyester fiber materials and mixed articles made of polyester fibers with other accompanying fibers, one has therefore switched to dyeing by the following methods:

1. According to the carrier dyeing method at boiling temperature;

2. After the high-temperature (HT) -Färbemethode at 120-135 ⁰ C for polyester fibers and their mixing products with cellulose fibers, or at 104-106 ⁰ C for polyester fiber / wool mixed product.

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In the case of colorations that occur in. Cooking temperatures are carried out and for dyeings in the temperature range of 104 - 106 ° C, the addition of carriers is necessary. Normally in dyeing in the temperature range of 120 -., Increased as much 135 ⁰ C, the diffusion rate of the "dyes that under these conditions, higher dye percentages without a carrier in less time pull on the polyester fiber However, it has shown that rbstoffe for certain F _a and for polyester fibers with poorer pulling properties, the use of smaller amounts of carrier is also advantageous in the HT process.

Combinations based on o-phenylphenol, chlorinated benzenes or phenols are used as carriers. These compounds are usually not physiologically harmless, i.e. they must not be inhaled or come into contact with the skin come and must also be removed from the wastewater as completely as possible, because they are only incomplete or at all are not biodegradable.

It is therefore made for reasons of health protection and from For reasons of cost when dyeing and cleaning wastewater, the desire to use polyesters primarily based on terephthalic acid and e.g. To create ethylene glycol or 1,4-bis (hydroxymethyl) cyclohexane, which can be stained carrier-free.

The work in this field is very varied and numerous. For example, attempts have been made to incorporate terephthalic acid and ethylene glycol and / or 1,4-bis (hydroxymethyl) cyclohexane into the polymer chain to incorporate other dicarboxylic acids or other diols, thereby enhancing the internal structure and crystalline structure of the Fibers to disrupt and loosen up, making the dyes easier can penetrate the inside of the thread. In this case, for example, minor amounts are used to vary the dicartaonic acid component of sebacic or adipic acid, 2,6-naphthalenedicarboxylic acid, 4,4 · - Diphenyldicarboxylic acid or 2,5-dimethoxyterephthalic acid is used.

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Suitable diols for cocondensation have also been found Ethylene glycol and 1 ^ -Bis-HydroxymethylJ-cyclohexa ^ propanediol -1.3 or -1.2, 1,4-butanediol or dioxethylated hydroquinone or dioxäthylated ρ, ρ'-Dioxi-diphenyl-dimethyl-methane proved.

These dicarboxylic acids and / or diols are condensed into the polyester under the usual conditions and lead to copolyesters with more or less improved dyeability.

However, fibers made from copolyesters produced in this way often leave something to be desired with regard to their textile-technical properties left over.

It has now surprisingly been shown that threads and fibers, which consist of polyesters of terephthalic acid and, in addition to the usual glycols, a dicarboxylic acid or a glycol with acidic ones Groups and besides 1-10 percent by weight, preferably 3-7 percent by weight bisethoxylated 2,2-bis- (4-hydroxyphenyl) -propane (called bisphenol A) of the formula

HO-CH ₂ -CH ₂ - 0- \ S) C ^ _ ^ · O-CH ₂ -CH ₂ -OH

contain, show such good dyeability that they can be dyed in a basic carrier-free manner and also have excellent textile-technical properties Possess properties.

The invention therefore relates to threads and fibers made from terephthalic acid copolyesters, which contain acidic dicarboxylic acids and / or glycols in chemically condensed form, which are characterized in that the terephthalic acid copolyester 1 to 10 percent by weight of the glycol of the formula

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HO — CHp — CHp — O (_) C ν ι yj— viip— ν / Αχό "

contained in chemically condensed form.

The particular advantage of these fibers is that they Carrier-free staining can be done with both dispersion and basic dyes. There are thus many possibilities given to process and dye these fibers in a mixture with 'fibers from unmodified polyesters and through a additional basic coloring, which only colors the fibers according to the invention, to achieve special color shades and color combinations.

Furthermore, it is possible to use beautiful light-dark shades to achieve these fiber blends, because dyeing without a carrier the fibers made from the unmodified polyester, e.g. from terephthalic acid and ethylene glycol or terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane, cannot be dyed as deeply as the fibers of the invention.

The threads and fibers according to the invention are obtained by spun a terephthalic acid copolyester, which is 1 to 10 percent by weight of the glycol of the formula I acidic in addition to customary glycols Contains glycols or dicarboxylic acids carrying groups in chemically condensed form and the threads obtained in known Way treated.

It has been shown to be particularly advantageous to have such Spun polyester, which in addition to 1-10 percent by weight, preferably 3-7 percent by weight of the glycol of the formula 11-10 percent by weight, preferably 2-8 percent by weight of 5-sulfoisophthalic acid as a compound bearing acidic groups in chemically Contained in condensed form.

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The polyesters of which the threads and fibers according to the invention are made preferably contain one as the main glycol component Glycol from the series ethylene glycol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-butanediol, in particular one of the first two mentioned.

In addition to terephthalic acid, the terephthalic acid copolyesters can also contain minor amounts of other dicarboxylic acids, such as hexahydroterephthalic acid, Contain adipic acid, sebacic acid and / or isophthalic acid.

The production of polyesters from terephthalic acid and for example Ethylene glycol or 1 ^ -Bis-ChydroxymethylJ-cyclohexane and 1-10, preferably 2-8 percent by weight, based on the total copolyester, of the sodium salt of 5-sulfoisophthalic acid and 1-10, preferably 3-7 percent by weight, based on the total copolyester, of bisethoxylated bisphenol A takes place according to a method known per se. The starting point is usually dimethyl terephthalate and the sodium salt of 5-sulfo-dimethyl isophthalate from and esters with bisethoxylated bisphenol A and the corresponding glycol, choosing the desired ratio of the components. This is followed by the pre-condensation and polycondensation to form the high molecular weight copolyester. This one gets in water too spun off a monofilament and this is then granulated. These granules are then melt spun.

The melt spinning process then closes in a known manner for the production of the threads and fibers according to the invention the steps of stretching, fixing, if necessary. Frizziness and cutting to stack length.

As a variation it should be mentioned that instead of the bisethoxylated Bisphenol A is the bisethoxylated 2,2-bis- (2,5-dimethyl-4-hydroxyphenyl) propane (called tetramethylbisphenol A) during manufacture of the polyester can be used.

A general procedure for making one according to the invention The copolyester to be used is roughly the following:

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Glycol- '
component Molar ratio
Dimethyl
terephthalate:
Glycol Transesterification
Temp. Duration
o _c hrs. 2-5 pressure Precondensation
Temp. Duration pressure
o _c . Hours. - 0.5- normal
pressure Polycondensation
'Temp. Constant pressure
O _n h 0.5-
5.5 <1 torr Ethylene
glycol 1: 1 to 1: 5 150-
220 2-4 normal
pressure approx.
250 - - 275-
295 0.5-
5.5 <1 torr 1,4-butane
diol
■ 1: 1 to 1: 2 150-
220 1-2 normal
pressure - - - 220-
270 0.5-
5.0 <1 torr 1,4-cyclo-
tiexan-
dimethanol 1: 1 to 1: 1.5 l8o-
280 From 8 at
waste
on nom
pressure id
ial- 295-
500

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An X-ray examination of the fibers according to the invention shows opposite Fibers made from pure polyester that they have a reduced proportion of crystalline areas. The cause this is due to the fact that the 5-sulfoisophthalic acid is condensed in and the bulky bisethoxylated bisphenol A molecule disturbs the morphological structure of the crystalline areas so much that only smaller lamellae or micelles are formed can, so that the proportion of amorphous areas increases at the expense of the crystalline areas. Because of this increased share in amorphous areas it is possible for the dyes to penetrate the fiber so quickly and deeply that the swelling effect of the Carriers can be dispensed with.

This makes the dyeing process less hazardous to health and the cost-intensive processing of the wastewater is no longer necessary.

A proportion of less than 1 % of the sodium salt of 5-sulfoisophthalic acid and 1% by weight of bisethoxylated bisphenol A in the copolyester gives only an insufficient increase in the dyeability, so that again carriers have to be used for dyeing. If more than 10 percent by weight of the sodium salt of 5-sulfoisophthalic acid and 10 percent by weight of bisethoxylated bisphenol A are added to the polyester made from terephthalic acid and ethylene glycol or terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane, the actual character of the pure polyester fiber becomes falsified too much. This can be seen from the lowered melting point and from the decrease in strength and abrasion resistance.

The threads according to the invention have the normal properties of those made from the unmodified terephthalic acid polyester, such as, for example, a strength of about 2.5-3.5 p / dtex at 20-25 % elongation. The color and whiteness of the fibers produced by the method described above are also unchanged. Just that

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250 255

Dye absorption capacity is so greatly increased that textiles made from these fibers can be dyed carrier-free. The relative viscosity of the terephthalic acid copolyester given in the description and in the examples is the ratio of Viscosity of an aqueous solution of the polyester in o-chlorophenol the viscosity of the pure o-chlorophenol, measured in each case in same units at 25 ° C in an Ubbelohde viscometer.

The dyeing tests show that fibers made from polyesters with predominant proportions of terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane or ethylene glycol and 1-10 percent by weight of the sodium salt of 5-isophthalic acid and 1-10 Containing percent by weight bisethoxylated bisphenol A, can be stained just as deeply and quickly without a carrier as fibers of the corresponding, unmodified polyester with carrier to be stained. For the comparative measurements, dyeing was carried out according to the following methods (cf. H. Ludewig "polyester fibers", academy Verlag Berlin, 1965, page 346).

Method 1

Before dyeing, the fibers are washed thoroughly. The liquor ratio is 1:20. When dyeing with Carrier ^, 4 g / l of a commercially available carrier (Levegalvü / PT from Bayer AG, Leverkusen) is added to the liquor. A pH of 4.5 to 5.5 is then set with monosodium phosphate and acetic acid. Then the liquor with 2 % of the disperse dye of the formula

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O OH

O NH

II

or the basic dye of the formula

III

added and the pH value adjusted if necessary. The dyeing bath is then in 20 minutes at 80 - 85 ⁰ C is heated and held for 15-20 minutes at this temperature. The swelling effect of the carrier takes place during this dwell time. In the course of 30 minutes the bath is brought to the boil and kept at this temperature for one hour. When the dyeing process is complete, the dyed material is rinsed warm and then dried.

Method 2

When dyeing without a carrier, the same dyeing process was carried out, however, no carrier was added to the liquor. The experiments reproduced in the examples show that the inventive Staple fibers can be dyed just as deeply basic or with disperse dye without a carrier as fibers of the unmodified corresponding polyester can be colored with carrier.

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In order to check these tests more precisely, the color valence, which consists of three color values and clearly defines a color, certainly. The reference system is the internationally agreed CIE system, which is synonymous with the norm-valence system DIN 5033 is. The color values in the CIE system are called X, Y and Z. For the measurement, the fibers are placed in a round cuvette pressed. The three-range color measurement method is then carried out using the ELREPHO filter photometer from Carl Zeiss, Oberkochen. This procedure consists of looking at the reflectance the sample with three special color measuring filters and off the remission values R, R, R in a simple way the color

χ y ζ

values X, Y, Z calculated according to the following formulas:

For standard illuminant C

X = 0.782 - R + 0.198 · R ₁₇ :

Λ Z

Z = 1.181 · R "

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η-

Example 1 ;

A reaction mixture consists of 2700 g of dimethyl terephthalate 2450 g!, ^ - bis-hydroxymethyl / cyclohexane (0.15 mol

Excess)

150 g of the sodium salt of 5-sulfo-dimethyl isophthalate

(5 oew. #)

150 g bisethoxylated bisphenol A (5% by weight ) 1.5 g isopropyl titanate

The reaction mixture is in an autoclave. The transesterification takes 1 hour, during which the temperature is raised from 200 to 260 ° C. The autoclave is under a pressure of 8 atm. The pre-condensation takes place for 50 minutes, the temperature rising from 26o to 295 ° C; the pressure is normal pressure. During the J> 6 minute polycondensation, the temperature rises to 300 ^° C. and the pressure is reduced to 1 Torr. It is then spun in cold water and granulated. The polyester has a relative viscosity of 1.82 and a melting point of 283 ^° C.

The granulate is spun using the melt spinning technique through a multi-hole nozzle to form threads with a single titer of 10 dtex and wound up at a speed of 1100 m / min. The filaments are in a damping channel of 170 ⁰ C in the ratio of 1: J5,2o, crimped in a stuffer box, cut-energized in hot air dried and then to staple fibers of 6o mm length. The fibers show a strength of 2.4 p / dtex, an elongation of 35 % and a boiling shrinkage of 2 %.

The fibers are now using the dyeing process described above (method 2 without carrier) with the basic dye of formula III colored. After the dyeing process has taken place

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the pasers have a deep blue hue.

The staple fibers are pressed into the cuvette and that above described three-area color measurement method carried out.

The color values found are: X = 18.1

Y = 13.2 Z = 32.6

If the entire manufacturing process is carried out with a granulate from the polyester made from terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane and only an addition of 5 percent by weight of the sodium salt of 5-sulfoisophthalic acid (relative viscosity 1.80) and also dyes these fibers as described above, but with the carrier Levegal PT (method 1), you also get deep blue fibers that are equally deeply colored from sight.

The measured color values are: X = 17.9

Y = 13.1 Z = 31.5

The fibers can then be made from predominant parts of the polyester from terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane and the addition of bisethoxylated bisphenol A and the sodium salt of 5-sulfoisophthalic acid without a carrier dye as well and as quickly as fibers made from polyester, which only contains the addition of the sodium salt of 5-sulfoisophthalate has to be stained with carrier.

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Mu lapiel 2;

KJn reaction chemistry consists of P.7G0 g of dimethyl terephthalate 27 ^{liters of} ethylene glycol (approx. 1 mol excess) 120 g of the sodium salt of 5-sulfo-dimethylisophthalate

(4 wt. #)

120 β bisäthoxyliertes bisphenol A (4 wt.%) 0.54 g of zinc acetate
0.54 g germanium oxide

The reaction mixture is in an autoclave. The transesterification lasts 3 hours at a temperature of POu ⁰ C. The precondensation then takes place at a temperature of 250 ⁰ C within 0.75 hours. The temperature is ^{increased to 275 °} C. for the polycondensation and the pressure is adjusted to about 1 Torr. The polycondensation has ended after 3.5 hours. It is then spun from the autoclave in water and granulated. The polyester has a relative viscosity of 1.70 and a melting point of 246 C.

The granulate is spun into threads using the technique of melt spinning through a multi-hole nozzle and these are wound up at a speed of 1100 m / min. The filaments are in a water bath of 95 ° C and in a subsequent damping canal of 170 ⁰ C in the ratio of 1: 3,2o, crimped in a stuffer box, energized cut in hot air dried and then to staple fibers of 60 mm length. The fibers show a strength of 2.5 p / dtex, an elongation of 35 % and a boiling shrinkage of 1 #.

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/ is

The pasers are now according to the dyeing process described above ' (Method 2, without carrier) colored with the disperse dye of the formula II. After the dyeing process has taken place the fibers have a deep blue hue.

The staple fibers are pressed into a cuvette and that above described three-range measuring method carried out.

The color values found are: X = 14.1

Y = 12.2 Z = 29.0

If the entire manufacturing process is carried out with a granulate made of polyethylene terephthalate, which only has an addition of 4 percent by weight contains the sodium salt of 5-sulfoisophthalic acid, through and stains these fibers as described above, but with the Carrier Levegal PT (method 1), one obtains also deep blue fibers that are equally deeply colored when looking at them.

The measured color values are; X = 13.9

Y = 12.0 Z = 28.6

The color values confirm that with the addition of bisäthoxylerten Bisphenol A has the same color shade without a carrier, i.e. a fiber that can be dyed without a carrier.

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Claims (1)

Claims; l _o) · filaments and parsers are from Terephthalsäurecopolyestem which contain acidic groups bearing dicarboxylic acids and / or glycols in chemically co-condensed form contained, characterized in that the Terephthalsäurecopolyester 1 to 10 wt.% of the glycol of the formula 0-CH ₀ -CH ₀ -OH contained in chemically condensed form. 2.) threads and fibers according to claim 1, characterized in that the terephthalic acid copolyester as the glycol component in addition to the glycol of the formula I, ethylene glycol, 1,4-bis (hydroxymethyl) cyclohexane and / or 1,4-butanediol in contain chemically condensed form. 3.) threads and fibers according to claim 1 or 2, characterized characterized in that the terephthalic acid copolyester in addition to 1 to 10 wt. # of the sodium salt of 5-sulfoisephthalic acid 1 to 10 wt. # Of the glycol of the formula I in chemically condensed Shape included. 4 «) Process for the production of threads and fibers by Melt spinning of terephthalic acid copolyesters and post-treatment of the threads thus obtained in a known manner, thereby characterized in that a terephthalic acid copolyester is spun which contains 1 to 10 wt. # of the glycol of the formula Le A 16.197 - 16 - 6 0 9.831 / 0789 HO-CH ₂ -CH ₂ -OH ^ j) c ' 0-CH ₂ -CH ₂ -OH in addition to the usual glycols and glycols or dicarboxylic acids bearing acidic groups in chemically condensed form. ..... Le A 16.197 - 17 - 609831/0789