DE1908173A1 - Fibers, threads and films made from polyesters containing paraffin sulfonate - Google Patents

Description

"Fibers, threads and films made from polyesters containing paraffin sulfonate"

The invention relates to antistatic fibers, threads and films made from modified polyesters.

It is an old problem that has not yet been satisfactorily solved Poljrester threads and films, which have a permanent antistatic behavior own to manufacture. Various approaches have been taken to solve the problem. This is how DAS 1 228 describes a "process whereby the polyester capped on one or both sides polymeric alkylene ethers having a molecular weight of at least 1300 are added in such amounts that they are used as separate phase. In order to achieve this, polyethers that still contain functional groups may be used add only shortly before processing, and the required concentrations are so high that considerable spinning difficulties appear. The use of polyethers that are capped on both sides is easier, but it is well known that these are manufactured Connections associated with considerable difficulties. The filaments and fibers produced by this process show one not inconsiderable deterioration of their textile behavior, which for example in increased yellowing and increased light degradation is expressed. The antistatic effect is no longer sufficient after several washes.

Essentially, however, one has dealt with the static charging of polyester structures by aftertreatment of the decrease finished products. For example, the Belgian patent specification 659 435 describes the aftertreatment of a textile material

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Made of polyester with aliphatic or aromatic substances containing sulfonate groups, the ester or ether groups as well may also contain polyether groups or longer hydrocarbon chains are known. The anti-static properties go but lost in the wash.

The addition of aromatic sulfonic acid esters without any further functional group in the production of polyesters is described in DAS 1 247 542. An antistatic effect however, these compounds were not observed in the polyester threads modified therewith. The sulfonic acid esters have the unpleasant property of easily forming free sulfonic acids by hydrolysis or alcoholysis, and this is the reason for the diglycol content of the polyester increases, making the polymer softening points unsustainable for textile purposes.

It is also known by admixing alkanesulfonates the electrostatic properties of moldings made of polystyrene (DAS 1 215 925), polyolefins (DAS 1 234 020) and polyvinyl chloride copolymers (US 2,973,440).

Surprisingly, it has now been found that fibers, threads or films made from fiber-forming polyesters have antistatic properties have, if they are used as modifiers 1 to 15 percent by weight, preferably 3 to 12 percent by weight, based on the polymer, of at least one alkali paraffin sulfonate with 8 to 30 Carbon atoms, preferably 13 to 18 carbon atoms, in the chain and with an average of up to two statistically in the molecule distributed sulfonate groups over the entire fiber, thread or film cross-section.

For the production of the modified fibers according to the invention. Threads and foils used can be obtained from, for example, polyester

a) terephthalic, isophthalic acid, 4,4'-diphenyl-dicarboxylic acid, 2,5-dimethylterephthalic, 5-sulfo-isophthalic acid, bis (-p-carboxyphenoxy) -ethane, Naphthalenedicarboxylic acid- (1.3), - (1.4), - (1.5),

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- (2,6), hexahydroxyterephthalic acid, cyclobutanedicarboxylic acid, Adipic acid, suberic acid, sebacic acid, decanedicarboxylic acid and sulfonyl-4'-dibenzoic acid or their ester-forming acids Derivatives or mixtures thereof and

b) diols or mixtures of diols, for example aliphatic diols such as ethylene glycol, propanediol (1.2), dutanediol (1.4), 2.2-dimethylpropanediol (1.3), cycloaliphatic diols such as cyclobutanediol (1.2) and cyclobutanediol (1.3) and ι .4-Dinethylolcyclohexan and aromatic-aliphatic diols such as 1.3 and 1.4 xylylene or bis (4,4'-hydroxyphenyl) -dimethylm ^<? than, 1.3 and 1.4-bis-hydroxyäthoxybenzol.

Also hydroxycarboxylic acids, such as p-Hydro :: ybenzoic acid eggs polyfunctional compounds such as triraellitic acid, trimesic acid, Pyromellitic acid, 5-Hydroxyisr ^ hthalic acid or Pentaerythritol, trimethylolethane- (1.1.1), trimethylolpropane- (1.1.1), 1.1.4.4-tetramethylolcyclohexane, 2.2.6.6-tetramethylol-cyclohexanol- (1) or their polyester-forming rivets can not be used will.

The acid portion of the polyesters are preferably used for the mixture consists of at least 9 ⁿ Kclprczent of terephthalic acid units as dicarboxylic acid and 0 to 10 mole percent, based on the polymer unit of at least one rnst of the other dicarboxylic acids listed above, the Gylkclantei] of at least 90 mole percent of ethylene glycol - or 1,4-Dimethylolcyclohexanresten and 0 to 1C mol percent, based on the polymer unit, of at least ^ a remainder of the other diols just listed.

It can also be up to 1.5 mole percent of the listed polyfunctional Alcohols and / or polyfunctional carboxylic acids, based on the polymer unit, are used in the transesterification or condensation.

The addition of the alkali paraffin sulfonates can be carried out at the beginning of the esterification or transesterification or at any time

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the polycondensation or by mixing with the finished polycondensation product take place.

The paraffin sulfonates are produced by known processes, e.g. that of Belgian patent 671 830 or that of U.S. Patent 2,263,312; they may contain small amounts of chlorine bound to the carbon chain.

The esterification, transesterification and polycondensation of the modified Materials are made according to known processes, using the usual catalysts, such as compounds of zinc, calcium, Manganese, germanium and antimony and optionally stabilizers can be used. If desired, pigments, Matting agents and / or crosslinking agents can be added in a known manner. Processing into threads, fibers or Filming is done according to standard procedures without any difficulty. It has been shown that products which are manufactured without a matting agent have a matt appearance, due to the very finely distributed alkali paraffin sulfonate particles visible under a light microscope, to have.

The fibers, threads or films according to the invention are distinguished by means of a permanent which is considerably better than antistatic fibers, threads and foils according to the state of the art antistatic behavior, which is also reflected in the resistance to laundry, dry cleaning and abrasion. In addition, they have an increased absorption capacity for cationic dyes and under certain conditions reduced capacity for disperse dyes.

The textiles, as well as the properties required for use as films, are different from shaped structures not in principle unchanged with paraffin-sulfonate-modified polyester. This makes it possible to use the invention Use fibers and threads for all textile areas. For certain Areas of application is the different absorption capacity for dyes for differential dyeing types in particular

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remarkable.

To assess the antistatic effectiveness, a flat textile structure made of modified material was tested after storage for 24 hours in a normal climate with the aid of a tereaohmmeter from Siemens and Halske AG. the surface resistance (Mi?) , as well as by means of a field strength measuring device according to Prof. Dr.-Ing. Schwenkhagen (Textilpraxis 11/12, 1147 / J95] J) determined the frictional charge (V / cm) after rubbing the sample against knitted fabrics made of polyamide, polyacrylonitrile and polyethylene terephthalate. In addition, after rubbing against cotton, the sample was held at a distance of 1 cm over finely divided cigarette ash and it was observed whether the ash was attracted or not. Since this so-called "ash test" often reacts differently than the friction test with the help of field strength measurement, it was included in the assessment.

Washing was done in a household washing machine according to the instructions with commercially available detergents, then rinsed according to instructions and air-dried.

In contrast to threads, fibers or foils made from unmodified materials Polyester, the affinity of the threads, fibers or films according to the invention for cationic dyes is increased. These can e.g. belong to the triarylmethane, rhodamine, oxazine, thiazine and phenazine series. The mentioned types of dyes can be used even increase if carriers such as chlorobenzenes, methylnaphthalenes, methyl salicylate and phenylphenols are used in the dyeing process will.

On the other hand, the dyeability of these modified fibers is reduced when using disperse dyes compared to fibers 'unmodified KLyesters decreased. With increasing concentration of alkali paraffin sulfonate in polyester does the drawback? like these dyes depend on the fibers. This effect is special strongly pronounced when with carriers or at around 12cffcdiE

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Carrier is colored '. The antistatic effect also persists the staining.

The present invention is illustrated in more detail by the following examples. . ^r

The relative viscosity (^ _re i) is applied to one percent solutions of the polyester in Phanol-tetrachloroethane (weight ratio; 3 ': 2) at 25 ⁰ C. . :. ■

Example 1 ; . \ -..- ■ -.

1.1 A mixture of 28.5 kg of dimethyl terephthalate, 23 kg ethylene glycol, 2.5 g of zinc acetate, 1.0 g of calcium acetate and 1.5 kg sodium paraffin sulfonate 7 (C .., to C * _s) is under /.-Rühren to 225 ⁰ C. and methanol is driven off via a column until the cleavage has ended. Excess glycol is then distilled off by increasing the temperature. After addition of 7.2 g of antimony trioxide and 2.64 g of phosphorous acid, the temperature of the melt 7 is within 105 minutes 275 ⁰ C erhöht'und the pressure to 0.1 to 1 Torr lowered. After a total of 4 hours, calculated from the start of the vacuum program, the polycondensation, which proceeds with elimination of ethylene glycol, has ended and a polyester of spinnable molecular weight has been formed.

"■■ - ■■■ -o-The colorless condensate has a softening point of 257 C ■ and a relative viscosity of 1.812. The> sulfur content is $ 0.5. ^" ■ '/ - \>

1.2 The polycondensate is at a spinning temperature of 28Q ⁰ C through a 24-hole spinneret with a take-off of 1Ö0Q m / min-. spun and then stretched 3.65 times as usual *. To obtain filaments having a tear strength of 4.2 ■ p / dtex and an elongation at break of 30.2 ° / o of _a

Example 2;

Analogous to the method of Example 1.1, initially unmodified

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adorned polyethylene terephthalate produced, in which, after the end of the polycondensation, 5 percent by weight of sodium paraffin sulfonate (C .., to C ^ ₈ ) are entered under nitrogen and stirred in at a pressure of 50 torr for 30 minutes. The colorless condensate has a softening point of 257 ° C. and a relative viscosity of 1.712 and is spun as indicated under 1.2. When stretched 3 »65 times, the threads have a tensile strength of 3.8 p / dtex with an elongation at break of 31.5%.

Example 3: .-.

Analogous to the process of Example 1, unmodified polyethylene terephthalate with a relative viscosity of 1.888 is prepared and processed into chips after the polycondensation has ended. The polyethylene terephthalate chips obtained are dried and _{mixed with 5 percent by weight of sodium paraffin sulfonate (C 1} to Cjq) in a mechanical mixer and then spun as specified under 1.2. After drawing 3.65 times, the threads have a tensile strength of 3.9 p / dtex and an elongation at break of 19 »6 °.

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Examples 4 to 10: ^:

In Examples 4 to 10, the concentrations of sodium paraffin sulfonate varies. The values for polymer production, the textile data of the threads and the results of the electrostatic Measurements for these examples are summarized in Table I together with the values from Examples 1 to 3. V

Table I see page, n

Example 11:. ,

1. A mixture of 475 g of dimethyl terephthalate, 760 g of 1,4-dimethylolcyclohexane 3 ecm of a 15 percent by weight solution of KHTi (OC ₄ Hg) ₆ in butanol and 25 g of sodium _{paraffin sulfonate (C 15} to C ₁₈ ) is brought to 200 with stirring Heated to 240 ° C and driven off through a column of methanol until the cleavage is complete. The temperature is then slowly increased from 270 to 305 ° C. in the course of 60 minutes at 1 torr and kept at 305 ° C. for 25 minutes. A light crystalline polyester is obtained, depending on the relative viscosity.

= 1..65 and a softening point of 278 C. -

2. The polycondensate is spun as indicated under 1.2 and stretched. . ■ "-."; "";

3. The electrostatic measurements are carried out and a. Surface resistance of 3000 / mS ^ T and friction charges in £ ~ V / cm / against polyamide of -253 against polyacrylonitrile of +322 and against polyethylene terephthalate of -302. Ash is: not attracted.

Example 12:. :

1. A mixture of 877.5 g of dimethyl terephthalate, 850 g of ethylene glycol, 72.5 g of dimethyl adipate, 0.765 g of magnesium acetate and 50 g of sodium paraffin sulfonate (C ₁ to C ₁₈ ) is transesterified as indicated under 1.1 and after adding

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0.260 g of antimony trioxide and 0.260 g of phosphorous acid polycondensed.

A light crystalline polyester is obtained with a relative viscosity ^ _rel = 1.766 and a softening point ■ of 24O ⁰ C.,

2. The polycondensate is spilled as indicated under 1.2 and stretched.

3. The electrostatic measurements and a surface resistance are carried out on the knitted fabric according to the methods given of 800 / ~ MS2_7 as well as frictional charges in / "" V / crnJ found against polyamide - 71 against polyacrylonitrile +219 and against polyethylene terephthalate - 155. Ash is not attracted.

Example 15;

1. A mixture of 918 g dimethyl terephthalate, 760 g ethylene glycol, 0.083 g zinc acetate, 0.033 g calcium acetate, 32 g sodium 5-sulfoisophthalic acid dimethyl ester and 50 g sodium paraffin sulfonate (C., to Cg) is transesterified as indicated under fT. Then, after adding 0.24 g of antimony trioxide and 0.088 g of phosphorous acid, polycondensation is carried out. The colorless condensate has a softening point of 251 ^° C. and a relative viscosity of 1,801.

2. The polycondensate is spun as indicated under 1.2 and stretched. .

3. The electrostatic measurements are carried out on the knitted fabrics produced from the threads according to the specified methods and a surface resistance of 1000 / Mü27 and Frictional charges in / ~ V / cm7 against polyamide of - 107, against. Polyacrylonitrile of + 55, and against polyethylene terephthalate of - 98 found. Ash is not attracted.

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Example 14; ■. -

1. A mixture of 950 g of dimethyl terephthalate, 710 g of ethylene glycol, 30 g of 2,2-dimethylpropandioi- (1.3), 0.083 g of zinc acetate, 0.033 g of calcium acetate and 50 g of sodium paraffin sulfonate (C. ~ to C ^ ₈ ) is converted as indicated under 1.1. ■ esters and polycondensed after adding 0.240 g antimony trioxide and 0.088 g phosphorous acid. The light-colored condensate has a relative viscosity #n -y of 1.795 and a softening point of 25T ⁰ C-. _:

2. The polycondensate is spun as indicated under 1.2 and stretched. , ':

3. A knitted fabric is made from the threads and then made the electrostatic measurements according to the method given carried out. For the surface resistance, 1000 / ΜΩ7> for the frictional charges; in / T / cm / are against Polyamide - 4-37, against polyacrylonitrile + 201 and against polyethylene terephthalate - 186 definitely. Ash is not attracted.

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Table I.

Values for polymer production, textile data and electrostatic measurements

Example Addition Weight Addition
No. . . f ° time

CO OO CO

liatrium- 5
parafG »
sulfomt
(C ₁₃ to

ti

(t

Il Il Il Il Il

5
4th
3
2
1

10
H

-irel. Tear tear expanded upper Reibungsladuhg / V ^T CM7 ash '"poly strength strength Elong. Ceutical area-test against poly' * 'condensed k £ it Ιψ Ι point contradictory Poly Poly ätlyÜBn . sat * / p / dtex7 / C7 stand amide acryl- ter-

ißSU rftrü phtha-

lat

z. Transesterification

η.PoIy condens.
on chips
Kenxed
analogous to 1
. »2
" 1
"2
■ "2

1,812

1,675

1,540
1,745
1,777
1,728
1,794
1,822
1,863

30.2 257

28.0
21.2
.33.5
32.3
27.6
28.7
27.5

4000

31.5 257

256
261
260
261
260
252
252

200
300

300

1000

80000

600000

50
10

-334

-217 -635

-597 +100 + 60 -568 -568 0 5

+140 -184

+468 -130 +618 -451

+631 +185

-

-

-451 ~ +

-35.2 + -100 -367 -468 0

Comparison:

Natural cotton

Polyethylene tere-

phthalate

+ = 'does not look'
- = attracts

χ with Dixan

20000
oo

-750 -2200

+1 +1 100

-250 -1500

++) = commercial product from Henkel (Düsseldorf) * = The spin breakdown varies between γ ■, 0.03 and 0.1

CD O OO

Table II

additive

Washing and dyeing fastness of the antistatic

Amount of type of laundry
/Gew.2°7 or coloring

Number of surfaces Frictional charge / V / cm / Ashed » Washes / mSc_7, Poly- Poly- Poly- test

amide acrylic ethylene nitrile terephthalate

Sodium paraffin
sulf onate
(C ₁₅ to C,

Il Il I? Il

ft

5 5

5 10

10 10

Washing machine

according to regulations
with Dixan

20 30 10 20

30th

cation.
coloring

000

000

000 000

000

, 100,000

000

;, 30 0Ό0

" :. 6 000

-134

-

-145 -367 -267

-401 -284

-129

-

+ 1-63

- + 125

+ 217-331

-141

-185 -100 +

-95

-217

ro

^: + '= does not attract ■,' ■ '"· ; ■ ■ ';'..' ■. ·· ■; ■; '.' ■, ■■ '. ■. ■', ■; ,, ,,, '■ ■ · ■ ".' ■ ■ ^■: ■ / ■ ',' / ■■. : ■. '"■ ++ = commercial product from Henkel, Düsseldorf. ■;

+++ = was colored with 2 # of the dye Cl. Basic Yellow 13 (Color Index, 2nd edition '"■. ■., Vol.> 1, p. 1622) V :: ¹ -; ■' ■■. ■■" ■ ν.:; .''- ¹ · '■■■ V; - ^ ... ■' ■:,. ''.;['■:' ■ ','. '■] -: ".-'. ' ^: · - ■ '' ■., '... ^! ,,,' = was dyed with 2 fo of a dye with the constitution ^: \;

CN '

CH ₀ -CH ₀ -COQCH;

__ CO

/ 195 £ 7 ο

: .. ■■. ■;. ■■■. .cx> ^:

CHo-OHo-

p — GOQCH ^

: - ■■ -_ 43 ---- .; ■■

Example 15:

15.1 Five parts of the threads in Example 1 are for an hour "dyed at 98 ⁰ C in a bath containing the following components:. 200 parts of water, 0 * 1 30 parts follow acetic acid, 0.8 parts of 2-methylnaphthalene and 0, 1 part of a cationic dye "of structure

Cl

^GH 3. ^e 6 ^H 5

CH

The. orange coloration obtained is washed with a detergent of the type of Äthylenoxidpolyadditionsprödukte 30 min. at 60 ⁰ C. It has excellent dimensional and rubbing fastness. "_. ^., ~ - ~ - _: -

15.2 If you use a dye instead of the dye listed above those of the following structure

Cl

this gives a real blue color.

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19Ö8173

15.3 The dye

CH ₂ -CH ₂ -Cl

—Ν -

causes a deep, real red color.

15.4 With a dye of the following constitution

j CH = CH-NH-CrL

C-GH,

Cl

¹ a yellow color is achieved. .-.- "- ■

Example 16; -

2.5 parts of a knitted fabric consisting of strips of polyethylene ■ ferephthalate and polyethylene terephthalate, which with; 5 ΐ% sodium alkanesulfonate is modified, are colored in a bath that contains the following ingredients: 200 parts of "water, 0.016 parts of concentrated sulfuric acid, 0.8 parts of 2-methylnaphthalene, 0.48 parts of a dispersant based on the." Alkylbenzenesulfonate and 0.05 part of a dye of the structure -

00 9837/2 187

HII ₀ O OH

OH 0

Han heated within 30 minutes to 98 C and dyed for 1 hour at 98 ⁰ C.

: J. and f.

The coloration obtained is for 30 minutes at ^ O C with eJn ^ r Washed solution, which contains the following ingredients:? 0O parts 'Water, 0.2 parts of a non-ionic detergent from the Class of oxethylated alkylphenols and 0.14 parts of soda.

This gives a true blue color, the aur on the strip: unmodified polyethylene terephthalate much more intense ir / ¹ than to the strip of the sodium Älkansulfanat modified polyalkylene terephthalate.

Eel_Use of the dye

/ 0

OCH

0 NH.

a red-violet color is obtained.

0 0 9 8 3 7/2167

BATH ORIGINAL

Claims (3)

- 16 - ■■ .; ..; ■;. ■ - ■;., ■ .- ■ - ■;.,.; ■■; Claims: '_ _ :: -; i ■' -. '■ _ 1. Antistatic fibers, threads or films made from fiber-forming Polyesters and a modifying agent, characterized in that the polyester fibers, threads or films as modifiers 1-15 percent by weight, preferably 3-12 percent by weight, based on the polyester, at least an alkali paraffin sulfonate with 8-30 carbon atoms, preferably 13 to 18 carbon atoms, in the chain and with on average up to two sulfonate groups statistically distributed in the molecule over the entire fiber ^ thread or film cross-section distributed included. 2. Antistatic fibers, threads or films made of polyethylene terephthalate, at least 90 mol percent, based on the polymer, of recurring units of the formula _v C-OCH ₂ CH ₂ -O- '.. ■■ -. and to 0-10 mole percent, based on the polymer, of recurring Units of another organic compound which has at least two ester-forming groups in the molecule, and a modifier, characterized in that the polyethylene terephthalate fibers, threads or films as Modifying agents 1-15 percent by weight, preferably 3-12 percent by weight, based on the polyester, at least one Alkali paraffin sulfonate having 8-30 carbon atoms, preferably 13-18 carbon atoms, in the chain and with in the middle Up to two sulfonate groups statistically distributed in the molecule, distributed over the entire fiber, thread or film cross-section contain. 3. Antistatic fibers, threads or films made of a polyester, which is at least 90 mol percent, based on. Polymers, made up of repeating units of the formula 0 0 and to 0-10 mol percent, based on the polymer, of repeating units of another organic " ^r erbir5: ^] τ which contains at least two ester-forming groups in the molecule, .r --- · and a modifying agent, thereby identified. that the fibers, threads or films made of the polyester as modifiers 1-15 percent by weight, r ^^^ ugEV / ein = 3-12 percent by weight, based on the polyester, at least "vr of an alkali paraffin sulfonate with 8 - ^ o carbon atoms, preferably 13 - 18 carbon atoms, in the chain and with an average of up to two statistically distributed sulfonate groups in the molecule, distributed over the entire fiber, thread or foil cross-section. 009837/2167 ßAD