DE1217915B - Process for changing the properties of molded articles made from high polymer polyesters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

D 06 m

German KL: 8k-2

Number: 1217 915

File number: F 33508IV c / 8 k

Filing date: March 25, 1961

Open date: June 2, 1966

The subject of the main patent 1044 756 is a process for changing the properties of molded structures made of high-polymer polyesters of the polyethylene terephthalate type, whereby compounds which have a swelling effect on the molded structures and which do not react with the polyethylene terephthalate under the process conditions, in substance or at normal or moderately elevated temperatures, are applied to the molded structures applied in solution in organic solvents and allowed to diffuse in at elevated temperature, optionally in a steam atmosphere. The process can also be carried out in such a way that the application of the aqueous substance and the thermal aftertreatment are carried out in one operation by heating the shaped structures in the swelling substance or in its non-aqueous solution. In this process, temperatures of up to approximately 200 ^° C. are used.

The additional patent 1151 780 relates to a further embodiment of the process of the main patent, which consists in the fact that the properties of shaped structures made of high-polymer, linear polyesters from polybasic acids and polyhydric alcohols, in particular from six-membered carbocyclic polyesters, z. B. of the polyethylene terephthalate type, can change in an advantageous manner if the formed structures for a short time at temperatures above 200 ° C, in particular above 220 ⁰ C, preferably at temperatures close to the melting point of the material to be treated, with such chemical substances, which have a swelling effect under the process conditions, but without reacting with the polyester material, treated in such a way that these substances only penetrate the surface of the material to be treated, but the interior of the material remains unaffected.

In a further embodiment of the method of the additional patent 1151 780 has now been found that one can further improve the properties of synthetic fibers made from high molecular weight linear polyesters of polybasic acids and polyhydric alcohols, if the action for 10 ~ ⁴ to about 5 seconds, one at a makes thread tension so low that the threads shrink by 5 to 35%. It is achieved in that the treatment agent penetrates more easily into the threads and between the threads, which plays a major role in the treatment of thick fiber cables, which consist of thousands of individual capillaries, in order to achieve a uniform treatment. The treatment effect, that is, the improvement

Procedure for changing the properties
of molded structures made of high polymers
Polyesters

Addition to the additional patent: 1151780

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M.

Named as inventor:
Dr. Rosl Kretsch-Hothum,
Bobingen near Augsburg

the dyeability, under otherwise completely identical conditions, the greater the lower the thread tension is and vice versa. Apparently it is the molecules of the substances involved not possible to penetrate sufficiently into the surface of strongly tensioned threads. As is described in the additional patent 1151 780, can be achieved by using very short contact times, that the treatment effect is essentially limited to a thin surface layer of the threads remain. A thread bundle with a titer of 300/140 harbors the optimal thread tension at which it is expedient is being worked, e.g. B. between 0.1 and 8.0 g. The threads are at the low thread tension given the opportunity to shrink during the treatment, whereby by varying accordingly this tension and thus the permitted shrinkage eliminate high values for the shrinkage of the finished thread can be adjusted as they are for further processing in weaving and Knitting are required.

The compounds mentioned in the main patent 1 044 756 and additional patent 1151 780 are used as treatment agents into consideration, insofar as they have a swelling effect under the process conditions and with the Polyester material does not react chemically, d. H. therefore, contain no reactive groups. In particular

others are esters, ethers, ketones, nitriles, hydrocarbons and similar connection types. The following are to be mentioned in detail: Diphenyl, tetrahydro-

609 577/411

3 4

naphthalene, chlorobenzene, diphenyl ether, glycolbutyl 4.0% and a thermal shrinkage (200 ⁰ C) of

ether, ethyl a-naphthyl ether, formaldehyde diphenyl - 2.5 to 6.0%.

acetal, sebacic acid dimethyl ester, sebacic acid - It is also within the meaning of the invention if in

ethyl esters, the corresponding esters of azelaine or, in special cases, the threads after the treatment

Suberic acid, benzophenone, adipic acid dinitrile and others. 5 can be stretched again to avoid any subsequent

Instead of uniform chemical compounds, shrinkage of those woven or knitted from them

can also allow mixtures of several compounds to be used during fixation processes. the

be applied. Re-stretching takes place in a manner known per se

The treatment agent is applied in a manner.

the manner indicated in the additional patent 1151 780. io It is useful to use stretched polyethylene so you can z. B. the material to be treated by terephthalate threads with lower viscosities, z. B. let a bath, which contains the treatment agent of the specific viscosities 0.450 to 0.700 and whose temperature is as constant as possible if threads with particularly good dye content are used. In order to achieve the required short contactability, which also has no or only a slight puffing effect, the time required for polymer and treatment agent to be achieved, the immersion distance is selected to be short, e.g. E.g. B. staple fibers. (The specific one listed here is between 0.5 and 10 cm. The take-off speed, viscosity in a 1% solution of the polyness is more appropriate in the present case because of the ester in a solvent mixture of 60 parts with low thread tensions - phenol and 40 parts Tetrachloroethane at 25 ⁰ C is chosen to be smaller than that determined in the additional patent 20.)

1151 780 described procedure, namely with the present method it is possible between about 10 and 100 m / min. However, by varying the viscosity of the polyester raw material, the material to be treated can first be soaked with the substance, by appropriate selection of the treatment agent and then through the treatment agent through the treatment conditions and the heated bath of the shrinking polyethylene terephthalate thread . This mode of operation has different textile technological properties and is particularly useful when producing from several individual dye images. It is threading existing aggregations such. B. Cables are particularly valuable that the process allows it to be treated or yarns. It is a matter of achieving very good dyeability, so that the scope of the inventive concept of the present treated threads without a carrier in dark shades of process, if the treatment agent can be dyed,
possibly in a low concentration on the fiber. ^ ₁₁
material and then apply this to other Example 1
Way, e.g. B. heated by infrared radiation or hot air Endless, fixed threads made of polyethylene terephthalate to the temperatures in question. 35 with a titer of 400/200 are left between two rollers -If you pass the threads directly through the heated trios, the first of which is running at 27.5 m / min, and treatment agent, it is advisable to use the second at 25.0 m / min, moved to pass through a bath temperature range between 200 and 250 ° C, which was heated to 23O ⁰ C and with Sebacinsäurearbeiten. The thread is left in the desired dimethyl ester. The immersion distance of the threads shrink th way. However, if you bring the loading 40 is 4 cm, the thread tension 6 g. Appropriate action means in the cold on the threads and the infeed and outfeed speed, the heating and shrinking of a thread in the bathroom can shrink by 10%. After this hot air zone or by transferring over heated treatment, the threads pass through a cold methanol metal surface, so it is expedient to choose a bath with an immersion distance of 75 cm in length and treatment temperatures between 250 and about 300 ° C. 45 are then wound up.

Removal of excess treatment- The threads obtained are with disperse colorant can be dyed very well by washing out with appropriate materials without a carrier. While the Washing baths that use water, with or without detergent, dye uptake of the untreated threads only or organic solvents, contained or accounted for by 26.0%, the treated threads take 80.0% Drying processes. The washing process comes under 50 dye.

Circumstances of particular importance. It became solid- To determine dye uptake

put that in some cases the dyeability 20 g of the sample in question in 11 liquor with 3% of the

can be increased by a few percent if the bromination product of 1,5-diamino-4,8-dioxy-

a small part of the applied treatment agent anthraquinone (based on the weight of the goods)

is washed out again. This applies e.g. B. for the 55 1 hour cooked, then the rest of the

treatment with diphenyl for a subsequent dye in the liquor is determined colorimetrically and

Wash with petroleum ether or petrol. from this the dye uptake of the sample in percent

It is a further object of our invention to calculate the total dye used,
with the post-treatment process to improve. .
the dyeability at the same time a heat setting 60 B e 1 s ρ 1 e 1 2
carry out, through which the otherwise usual endless, unfixed threads made of polyethylene terephthermofixation by hot air or steam thalate of the titer 400/200 are superfluous with a Fadenais own operation. The thread tension of 0.75 g with an infeed speed is set in this case so that the polyester of 30 m / min, and a withdrawal of 25 m / min, and threads during the treatment sufficiently extend an immersion distance of 4 cm can shrink by at 22O ⁰ C. In the case of twisted threads, a heated bath of dimethyl sebacate is carried out and the twist is fixed at the same time. The fixed thread has, so that the threads in the bath can shrink by 20% after the treatment, a boiling shrinkage of 1.5 to. You then go through a 75 cm long bath

with cold methanol and are then wound up.

The dye uptake of the untreated threads is 29.0%, the dye uptake of the treated Threads, on the other hand, 78.0%; 2.8% was measured for the thermal shrinkage of the treated threads, for the Boiling shrinkage 1.8%. The threads were fixed at the same time during the treatment.

Example 3

Endless, unfixed threads made of polyethylene terephthalate with a titer of 400/200 are treated analogously to the procedure described in Example 2. However, instead sebacate the bath contains Terephthalsäuredibutylester and is heated to 21O ⁰ C. The treated threads have a dye uptake of 79.0% compared to 29.0% dye uptake of the untreated threads.

Example 4

Endless, unfixed threads made of polyethylene terephthalate with a titer of 400/200 are treated analogously to the manner described in Example 2. However, the treatment includes diphenyl sebacate place and is heated to 210 ⁰ C. The threads obtained have a dye uptake of 81.0% compared to 29.0% dye uptake in the case of the untreated threads. After washing for 1 minute with cold petroleum ether, the dye uptake increases to 86.5%.

Example 5

Endless, unfixed threads made of polyethylene terephthalate with a titer of 200/100 and a specific viscosity of 0.620 are treated analogously to the manner described in Example 2. However, instead sebacate, the treatment includes Terephthalsäuredibutylester and is heated to 21O ⁰ C. The treated threads have a dye uptake of 87.5%. They absorb so much dye that they can be colored deep black without using a carrier. They were also fixed at the same time during the treatment.

Example 6

Endless, unfixed threads made of polyethylene terephthalate with a titer of 200/100 and a specific viscosity of 0.620, the individual capillaries of which have a 5-star-shaped cross-section, are treated analogously to the manner described in Example 2. The bath contains terephthalic acid dibutyl ester and is heated ^{to 20 ° C.}

The threads obtained have a dye uptake of 82.5%. They can be left without any addition dyeing carriers black in an open dye bath. They are also involved in the treatment at the same time been fixed.

Example 7

Endless, unfixed threads made of polyethylene terephthalate with a titer of 100/50 are passed at a speed of 50 m / min through a cold bath filled with a 15% solution of dimethyl sebacate in methanol. The filaments are then dried and then long over a heated to 80 ° C drying drum, which is also at 50 m / min, running, in a 50 cm, led to 255 ⁰ C heated hot air duct and then discharged through a roller trio, with 40 m / min. moved so that the threads in the hot air duct can shrink by 20%. Then the threads are wound up.

The threads obtained take up 75.0% dye, the untreated only 29.0%.

Example 8

Endless, unfixed threads made of polyethylene terephthalate with a titer of 100/50 are treated analogously to the manner described in Example 7. As a treatment agent a 15% solution of terephthalic acid dibutyl ester in methanol is used.

The dye uptake of the treated threads is 78.0% versus 29.0% dye uptake of the untreated threads.

Claims (2)

Patent claims: 1. Further development of the process for changing the properties of shaped structures made of high molecular weight, linear polyesters made of polybasic acids and polyhydric alcohols by brief exposure to such chemical substances that have a swelling effect under the process conditions without chemically reacting with the polyester material, at temperatures above 200 ⁰ C, according to patent 1151 780 (addition to patent 1 044 756), characterized in that the action is carried out for 10 ~ ⁴ to about 5 seconds at such a low thread tension that the threads shrink by 5 to 35%. 2. The method according to claim 1, characterized in that unfixed threads are used and it shrinks during treatment and fixes it at the same time. Considered publications:
French Patent No. 1145 163;
British Patent No. 756 715. 609 577/411 5.66 © Bundesdruckerei Berlin