DE1044756B - Process for changing the properties of molded structures made from high-polymer polymethylene terephthalates - Google Patents

Description

Molded structures made of high polymer polymethylene terephthalates, especially those made of high polymer ethylene terephthalate, such as. B. fibers and foils, have, when subjected to a stretching process, a very dense internal structure. This shows e.g. in the fact that such fibers or structures thereof are formed under conditions such as those encountered when using Disperse dyes are customary in acetate silk dyeing and cannot or hardly be dyed.

One process for coloring high-polymer poly- ίο methylene terephthalates with acetate silk disperse dyes is to carry out the coloring in the presence of sources, so-called carriers (British patents 609 943 to 609948). The swelling agents are used in an aqueous solution or dispersion. They can be added to the dye liquors, but the high-polymer polymethylene terephthalates can also be treated in an aqueous liquor before the subsequent dyeing with the swelling agents. In general, the carrier processes at elevated temperatures is carried out up to 100 ⁰ C. The main disadvantage of this procedure is that, as a result of working in aqueous solution, the compounds used must be used in high concentrations in order to be effective. As a result of their volatility, especially with water vapor, considerable losses of active substance occur during the dyeing or pretreatment process, which make special measures necessary during the treatment. Due to the odor nuisance occurring as a result of the distilling off of the compounds, one is forced to work in special equipment or with the use of special protective measures.

From the British patents 697 983 to 697 986 are also methods for improving the dyeing Properties of fibers or fabrics made of polyester fibers become known, in which the textile material with aqueous solutions of inorganic compounds such as zinc chloride or lithium bromide or with Sulfuryl chloride is treated. The substances cause a superficial attack and a roughening of the Fiber. In this process, however, a strong hydrolytic damage to the fibers occurs, which with a Weight loss of the material is associated. The connections used must be replaced by an additional Wash process can be removed again before dyeing. As in the process relatively highly concentrated solutions are used, there are constant losses of substance that make the process uneconomical.

To enable staining with acidic dyes, which cannot be done in the presence of carriers alone is feasible, one has, inter alia, high polymer polymethylene terephthalates with small amounts of amino alcohols certain constitution at higher temperatures

to change the properties
of molded structures made of high polymer polymethylene terephthalates

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M., Brüningstr. 45

Dr. Ludwig Orthner, Frankfurt / M.-South,

Dr. Karl Horst, Hofheim (Taunus),

Dr. Rudolf Lademann, Frankfurt / M.-Unterliederbach, and Dr. Manfred Sander, Frankfurt / M.-Höchst,

have been named as inventors

temperature implemented. A not inconsiderable one occurs here Degradation of the high polymers. The transesterification results in an interruption, so that a Affinity for acidic dyes occurs, but this only has an effect in the presence of carriers in the dyebath comes.

It has now been found that the properties of molded structures made of high-polymer polymethylene terephthalates, in particular made of high-polymer ethylene terephthalate, can be modified in that compounds which have a swelling effect on the formed structures and which do not occur under the process conditions react with the polymethylene terephthalates at normal or moderately elevated temperatures in substance or in solution in organic solvents and applying them at elevated temperature, optionally in a Water vapor atmosphere, can diffuse.

For the purposes of the present invention, the compounds are initially used as swelling substances in question, which are generally referred to as carriers in the specialist literature (cf. e.g. Textil Age, Vol. 15 [1951], P. 32; British patent specification 609 943), provided that the compounds do not have any groups which, under the process conditions act on the polyester compounds and break them down. As such groups are primary and secondary amino groups.

Examples of compounds with a swelling effect are: diphenyl, tetralin, chlorobenzene, benzyl alcohol, BenzliydroL Diphenylether, benzoic acid, 4-chloro

809 680/522

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2-oxy-benzoic acid, chloronaphthalenecarboxylic acids, form- the polyester bonds can react, are the beealdehyde-diphenyl acetal, Glycol butyl ether. to choose conditions so that no reaction occurs.

In addition, sub- The optimal process conditions are the case

still punch a large number of other connections to be determined on a case-by-case basis.

are not used as carriers in the aqueous 5 If endless fibers can be used after the dyebath according to the invention, since they either equip a process, the treatment at a swelling effect can only be carried out in a non-aqueous medium or at a suitable point in the manufacturing process continuously at temperatures show above 100 ^° C. For example, may be carried out. But you can also mention the following: Dioxane, p-toluene sulfanide, caprolactam, required processes in a strand or roll or on the zoin, 4-ethoxy-phenyl-urethane, benzoylaminobenzoyl-io coil. Staple fibers can be treated as tow, flake methylglucamide, naphthoyl aminobenzoyl pentaerythritol, or yarn. If you want knitted fabrics or their derivatives oxyethylated to the OH groups. Subject tissue to the treatment according to the invention,

If you use substances with a swelling effect, you can use the swelling agent, for example, by foular compounds, the tertiary amino groups or quaternary dieren and subsequent squeezing or spinning off Contain ammonium groups, so is applied by the 15, which is then followed by the thermal drive according to the present invention, an improved action on suitable pass-through apparatuses of known art Can be dyed for acidic dyes of the high polymer construction or on the star frame. at Polymethylene terephthalate achieved without the application of the claimed method to films Degradation of the high polymer takes place. For example, one proceeds accordingly.

may be mentioned: diethylamine, tribenzylamine, 1-ct-naph- 20 The material treated according to the method shows under thoyl-aminoethyl-diethylamine, Ν, Ν-diethyl-N'-benzoyl- preservation of the physical properties an in ethylenediamine, p-benzamido-jS- (diethylaminoethyl) -benz- in many cases a significant improvement in the absorption amide, Terephthalic acid-bis- (diethylaminoethylene) -diamide, property for dyes, which by a loosening Tetraethylene glycol bis (j8-dimethylaminoethyl) ether, the structure of which is very likely in the Tetraethylene glycol - phenyl - dimethylamino - ethyl ether, causes 35 amorphous areas. One can therefore use the p-Benzoylaminobenzoylaminoäthyl-triethylammonium- according to claims treated structures with dispersion salicylate. dyes such as those used to dye acetate silk

It is sometimes advantageous to use mixtures of different colors, as is customary in acetate silk dyeing To use swelling agents for the process. Color process in deep tones. So far one was

Of course, the method 30 is forced to the success, either so-called carrier mitzuverwengemäß of the present invention, a possible direct or the dyes in a closed apparatus at even application of the swelling acting substances temperatures above 100 ⁰ C to carry out. Even with essential prerequisites. The compounds can be used as such or in the form of solutions in orga- 35 z. B. in the vat acid process or when applying niche solvents are used. The von / 5-Oxynaphthoesäurearyliden, show the demanding application of the substances can take place at normal or in the case of structures treated according to the moderately elevated temperature described above. Advantage.

To avoid a possible excess of swelling agent to fabric from the fibers treated according to the claims

remove, the shaped structures after the 40 can after the application of polymethylene terephthalates the swelling agent squeezed off or borrowed printing process, but without the use of flings. In many cases it proves to be advantageous for carriers to be printed.

this thermal aftertreatment in the presence of As already mentioned, swelling agents can also be

Steam, if necessary under pressure, can be used which has a tertiary amino group in the molecule One can also have the application of the effective sub-45. In such cases there is also an improved punch and the thermal aftertreatment into a dyeability for acidic dyes, d. i.e. those with the The process can be summarized in that the formed substances mentioned can be treated Structures in the swelling substance or in their both with disperse dyes, as they are, for. B. in the not heated aqueous solution. The thermal hand-Acetatseidenfärberei find use, after It is advisable to carry out a wash afterwards. 50 common methods, but you can also use

The thermal treatment can, in general, the case of dyes which carry acidic groups and water temperatures in the range between about 80 and about are carried out in many cases without the addition of carrier into a 200 ^0C. The duration of the treatment depends on the desired effect and constitution in deep shades of good wash fastness. Provided however the improvement of the other means used. If one and the same agent 55 is not dyeable enough for acidic dyes, the duration of the thermal treatment is heavily dependent on the temperature in the usual way with the use of swelling. At low temperatures, medium-colored. Further, in the Anetwa 110 to 13O ⁰ C, is required for carrying out the application of substances of acidic character to the procedure times, for example 10 to 30 minutes. The method described herein a significant improvement Applying higher temperatures, about 180 to 60 of the dyeability to basic dyes he-200 ⁰ C, so suffice, for example 20 to 60 seconds. aims.

If one considers the thermal treatment in the presence of furthermore in many cases in the treatment of the

performed by water vapor, one gets stronger material according to the present invention also effects, and mostly the treatment time can be achieved - improvement of the handle of the textile material is achieved,
shorten. Thus, through the selection of the conditions, one has it in hand. Besides the mentioned improvements in the properties and the means, the process can largely be adapted to the conditions of the earth equipment depending on the selection of the treatment means. increase in the value of the moisture absorption achieved

With the use of indifferent swelling agents one can become something for use in the clothing sector work in relatively harsh conditions. At source is desired. Improvements in anti-medication, which contain functional groups that can be achieved with 70 static properties. That claimed

ϊ 044 756

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Process brings a considerable amount of technical material, as described in Example 1, in low tones

step, since improving the properties of the dyed,

molded structure from high polymer polymethylene.

terephthalate from the fiber manufacturer in Example 6, which is always the same

Art can be done and the processor the application 5 1 part washed, dry, ^{fixed at 120 0} C silk

of additional tools or complicated apparatus made of polyethylene terephthalate is 10 minutes in 50 parts

doors or procedures are saved. Treated dioxane at 80 ⁰ C and then hung to dry. The silk treated in this way can, as in

Example 1 Example 1 described, with disperse dyes

lo be colored.

100 parts of a ^{fixed at 13O 0} C Polyäthylentere-

phthalate fibers are mixed with 1500 parts of a 3 "strength methyl Example 7

alcoholic solution of formaldehyde diphenyl acetate A strand of polyethylene terephthalate is for 5 minutes

impregnated at 6O ⁰ C for 3 minutes. Then the utes of the steam atmosphere over boiling dioxane

Goods squeezed off and dried. 15 suspended and then imposed. The strand can

The goods prepared in this way are then placed in an apparatus, as described in Example 1, in depth

brings, which can be evacuated and colored with a steam jacket tints,

is provided. In this damper the material is after. .

previous evacuation 15 minutes at 130 ^° C. Examples

Internal temperature (corresponding to about 3 atmospheres vapor pressure) 20 1 part of polyethylene terephthalate silk is 10 minutes in steamed with steam and after taking out 200 parts of dimethylanine treated at 100 ° C, dried, then squeezed off and treated with a 0.2 "/" soap

The fiber treated in this way can be washed cold with dispersion paint solution and dried,

fabrics without applying pressure or using the silk treated in this way can be coated with acetate silk

be dyed by carriers in deep shades by dyeing 25 dyes as described in Example 1

they are, for example, with 4000 parts of an aqueous dye.

liquor, the 2 parts of p-nitro-o'-methyl-p'-di - ^ - oxäthyl) - _{Beis iel} g

contains amino-azobenzene and 4 parts of soap, 90 minutes at ^

95 to 100 ⁰ C treated. 1 part of polyethylene terephthalate staple fiber is used in

_. . . _ 30 50 parts of a 10 ° / _o solution of polyethylene glycol,

± 5example Δ average molecular weight 200, in dioxane for 30 minutes

100 parts of a fixed at 130 ° C Polyäthylentere- 100 ⁰ C treated. The squeezed and with warm phthalatfaser be with 1200 parts of a 5% me- water flushed fiber can be with Dispersionsfarbthanolischen solution of benzoin 5 minutes at 6O ⁰ C materials deep and no matter stained by being treated for, squeezed out and dried. The material 35 as with 80 parts of dye bath, 0.08 parts of 1-methyl is, then impregnated for 15 minutes at 13O ⁰ C without steam-treated amino-4-iS-oxäthylamino-anthraquinone and 0.1 parts of soap and is a usable fiber , contains, treated for 1 hour at 95 ° C,
which can be stained well, e.g. B. in example 1
described way. Example 10

Example 3 _{γ Teü hei 13 (rc & dertes} polyethylene terephthalate

Yarn 100 parts of a fixed at 130 ⁰ C Polyäthylentere- is in about 50 parts of chlorobenzene for 5 minutes at

phthalatfaserwerdenmit200Teileneiner5% igenmethano- 130 ⁰ C treated. The still adhering chlorobenzene is

Lischen solution of 4-ethoxy-phenyl-urethane at 6O ⁰ C as described in Example 5, removed by washing,

treated, squeezed and dried. After a 45 The yarn treated in this way can be washed with acetate silk dye

Treatment in the steamer in the dye used in example 1 in deep tones,
wrote way at 130 ⁰ C within 15 minutes

the fiber is so impregnated that it is slightly dyed through. Example 11
can be.

50 1 part at 130 ⁰ C fixed polyethylene terephthalate yarn

.beispeü 4 _{is loaded in about 4Q Teüen tetralin for} 5 minutes at 150 ° C

100 parts of a ^{fixed at 130 0} C Polyäthylentere- is. The still adhering tetralin is, as described in the phthalate fiber with 1500 parts of a 2% metha Example 5, removed.

Nolic solution of 4-chloro-2-oxy-benzoic acid 30 minutes. The yarn treated in this way can be used in the im

th treated at 50 to 6O ⁰ C, subsequently squeezed off, 55 Example 1 described manner stain,
dried and, as described in Example 1, in one
Treated damper at 130 ⁰ C for 10 minutes. Example 12

The fiber treated in this way is suitable for all known ones

Staining procedures for disperse dyes without particular part 1 at 130 ⁰ C fixed Polyäthylenterephthalatgarn

Use of carriers or pressure equipment. 60 is treated in about 50 parts of glacial acetic acid at 115 ° C. for 2 minutes. The still adhering glacial acetic acid is mixed with lukewarm

Example 5 Rinsed with water. The yarn treated in this way can

with disperse dyes, as described in Example 1, dye 1 part of polyethylene terephthalate yarn fixed at 130 ° C.

is with a solution of 4 parts of benzhydrol in 8 parts of 65 Beismel 13

Soaked in dioxane. After squeezing and drying on

the air, the yarn is so treated as described in Example 1 1 part fixed at 130 ⁰ C Polyäthylenterephthalatgarn

described 15 minutes a loss at 13O ⁰ C off is set in about 40 parts of benzyl alcohol for 5 minutes at 13O ⁰ C. The yarn is then treated with 0.2 ° / ₀ sodium soap solution. The still adhering benzyl alcohol is ^{washed as at 50 0} C and can then with acetate silk dye 70 described in Example 5, removed. Treated like that

7 8

Yarn can be, as described in Example 1, in deep and then with acidic wool dyes in Coloring tones. stain strong tints.

Example 14 Example 19

1 part of at 130 ^o Cn3dertenPolyäthylenterephthalat- 5 1 part fixed at 130 ° C Polyäthylenterephthalatgärn games in 20 parts of polyethylene glycol from the throughput is about SO parts of a 10 ° / ₀ aqueous solution of tetra-average molecular weight 200 40 seconds at 180 ° C ethylene glycol-bis - (jS-dimethylaminoethyl) ether in toluene is heated, squeezed out and treated by rinsing with water for 20 minutes at 110 ⁰ C. The yarn is freed with polyglycol adhering to the surface. The so warm water rinsed and can be dyed both with acetate-treated silk, as described in Example 1, IO silk dyes and with acidic wool dyes in deep dyes with disperse dyes. can be colored in the manner described above.

Example 15 Example 20

100 parts of a fixed at 130 ° C Polyäthylentere- 1 part fixed at 130 ⁰ C Polyäthylenterephthalatgärn

phthalatfaser are mixed with 2000 parts of a 5% 15 in 10 parts of a 10% dioxane solution of Tetraäthylalkoholischen solution of 2 minutes tribenzylamine ethylene glycol - monoethyl ether treated at at 6O ⁰ C - phenyl - dimethylamino. It is then squeezed off and soaked at room temperature and then thermally aftertreated for 15 minutes, such as 15 minutes at 130.degree. described in Example 1, steamed at 13O ⁰ C.

A fiber impregnated in this way can be dyed with acidic wool dyes.
for example with 4000 parts of an aqueous dye liquor,
the 2 parts of a dye of the following formula: Example 21

1 part of a fixed at 130 ⁰ C silk of polyethylene terephthalate is impregnated phthalic 25 säurediphenylester in fine solution of 5 parts in 95 parts of methanol for several seconds, then squeezed "and, after evaporation of the methanol, steamed as described in Example. 1 leaves the fiber then dye yourself with acetate silk dyes in deep COOC ₂ H ₅ shades.

³⁰ Example 22

O NH- <.... _s > _A strand of polyethylene terephthalate silk is used in

20 times the amount of a 5% solution of phenoxyacetic anilide soaked in ethanol and then squeezed. After drying, the strand is, as in Example 1 described, steamed and then with

2 parts of formic acid and 1 part of a condensation a '0.2% soap solution washed. The silk can then be dyed with a product made of alkylphenol and about 13 mol of ethylene oxide, as described in Example 1, with acetate silk dye, without the addition of a carrier, for 90 minutes at 95 to fabrics in rich tones.
100 ⁰ C treated. 40 When working in the same way using

Example 16 p-Toluenesulfonic acid phenyl ester is also obtained

Silk, which, as described in Example 1, with acetate

100 parts of a polyethylene tere-silk dye fixed at 130 ° C can be dyed in deep shades,
phthalate fiber are made with a mixture of 1000 parts

an oily ethyl alcoholic solution of 1-a-naph- 45 Example 23

thoyl-amidoethyl-2-diethylamine and 500 parts of a

5% ethyl alcoholic solution of formaldehyde- 1 part of a polyethylene fiber fixed at 130 ° C

treated diphenyl acetal at 50 to 6O ⁰ C for 5 minutes. The terephthalate is 10 minutes at 110 to 120 ° C in 20 parts of material is squeezed off and dried. Treated after a dimethylformamide. After drying subsequent attenuation can, as described in Example 1, 50, the thus treated fibrous material with Acetatseidenfarbbei 13O ⁰ C one obtains a well-dyeable fiber. fabrics, as described in Example 1, in rich tones

_. . , . ^ y. to be colored.

Example 17

1 part of washed and dry silk on the polyethylene

terephthalate is in 200 parts of a 10% solution 55 A strand of silk made of polyalkylene terephthalate is in

of N, N-diethyl-N'-benzoyl-ethylenediamine in acetone of a 5 ° / _o solution of Bimethylphenäthylamin in

Treated at 100 ^° C. for 10 minutes. The strand is then heated to the boil for 10 minutes with dioxane and then

squeezed off and centrifuged for 15 minutes at 125 ° C in a dry ßend to the Tioclaie. The treated like that

cabinet tempered. The goods treated in this way are made into a silk can with acetate silk dyes or, as in

Washed cold water with O ^ o / o soap solution and, as described in Example 15, can be treated with acidic wool dyes.

Described in Example 15, are colored with acidic dyes.

^coloring - example 25

Example 18

10 parts of a polyathy-terephthalate fiber

1 part of silk from polyethylene terephthalate is carried out for 5 minutes 65 1 to 2 minutes in 3ΘΘ parts of a 5% solution of in a mixture of 100 parts of dioxane, 7 parts of a benzoic acid (| SN-nϊethy ^ benz57lafflino-ethyl ester) in dioxethylated (16 AeO) and quaternized palm kernel fat 100 ⁰ C treated. L% acetic acid ge-washed goods are treated in 400 parts of diamide at 1OQ ⁰ C - -The s © treated with amine and 5 parts) Terephtlialsäure-bis-fdiäthyläthylen. The skein is dyed boiling for 10 minutes, a liquor 90 minutes, which is as follows, as described in Example 1, steamed and: washed 70 is composed:

2 ° / ₀ (based on the weight of the goods) of the dye of the formula

HO '

SO "H

(see Schultz color tables, 7th edition, vol. 1, no.206) 3% (based on the weight of the goods) formic acid 85%, 3% (based on the weight of the goods) of an oxethylated

Alkylphenols (approx. 13MoIAeO),
20 g / l salicylic acid.

A deep red color is obtained in this way.

Example 26

A strand of a silk made of polyethylene glycol terephthalate is 10 minutes under pressure at 120 ° C in Treated methylene chloride. The material treated in this way can then be used with disperse dyes without use Color by carriers or printing in deep rich tones, for example in that described in Example 1 or 9 Art.

The same result is obtained if one carries out the treatment with chloroform at 9O ⁰ C.

Claims (2)

PATENT CLAIMS: 1. Process for changing the properties of molded structures made of high-polymer poly (methylene terephthalates), in particular made of high-polymer ethylene terephthalate, characterized in that that swelling compounds acting on the formed structure are produced under the process conditions do not react with the polymethylene terephthalates at normal or moderately elevated temperatures in Applying substance or in solution in organic solvents and using it at elevated temperature, optionally in a steam atmosphere, can diffuse. 2. The method according to claim 1, characterized in that the application of the effective Substance and thermal aftertreatment in one operation by heating the molded Forms in the swelling substance or in its non-aqueous solution. Considered publications:
German Patent No. 827,899;
British Patent Nos. 684046, 609 943
948, 697 983 to 697 986.