DE1619003A1 - Process for coating fiber-containing or thread-like substrates with a polymer - Google Patents

Description

'εrfahron for the D-layering of fiber or thread * .'like substrates with a polymer

The present invention relates to the coating of fiber-containing or filamentary, flexible substrates with a polymer under such conditions that damage to the substrates by the coating largely avoids and at the same time the substrates for their useful properties verlicrion vAorden. Such substrates are preferred ^ V / olle. for the purposes of the present invention are also understood products under substrates were prepared from the fibrous or filamentary materials, \ i ± e rovings, yarns, Kammziige, GeV / ebte or knitted "^ .G-'fa etc .. Further examples of fibrous materials such as paper, cardboard and the like .. thread-like substrates ;

Z .: A particular purpose of the present invention is to keratinous or. to coat keratinous fibers, with the coating is carried out with a polyamide film, k ink-containing pastes in this sense include in particular

008843 / 172fi

" BATH

VcLl fibers, as already stated above; became. The expression For the purposes of the invention, wool or wool fibers should be any kind of keratir-hal-jige fibers and, in particular, paocm include those from the pell of sheep, goats, llamas, Vil-: u: i j as, alpacas etc. are obtained, provided in the description nothing else is done.

It is known to use JSylon 610 with the help of grass surface polycondensation (iPP process) from hexamethylenediamine and To produce sebacic acid dichloride. The hexamethylenediamine is in water and the sebacic acid dichloride in one Solvents which are immiscible with water, for example carbon dioxide. /~S.L. Wittbecker and P.W. Morgan, J. Polymer Sci., 40, 289 (1959); P.W. Morgan and S.L. Kwolek, J. Polymer Sci. £ 0.299 (1959J7

This so-called IFP process was also used for the fungus-free finishing of wool. Wool soaked with an aqueous hexamethylene diamine solution is treated with sebacic acid dichloride in a water-immiscible organic solvent. The polyamide film formed at the phase boundary between water and organic solvents masks the scales of the surface of the fiber. The reason for this is the reduction in the fungal capacity of wool. The best anti-felting effects were achieved with nylon o10 örsielö. To achieve a sufficient anti-felting effect, a nylon layer of 1-2 ^c ß> / ~ RE Whitfiela, L.A., Miller and WL Wasley, Lexile Res. J., 3.1% ° 4 ( ¹ ^ ^c Dieees known process possesses for the technical

009843/1728 " ³ "

-O -

Carrying out goal ~? Felt free equipment of ', full some ^ uc ^ hurry. These "consist, is v / it borrowed in the I-iy & rolyseenpf indlicclceit des Sebacinsäurediehlorids "and in. the strong Deterioration of the grip of the equipped ', / olle.

The present invention is based on the object of avoiding the obvious disadvantages which are given by the use of acid chlorides and which are known to the person skilled in the art, and which arise, particularly in the treatment of natural fiber-containing or thread-like material. as mentioned above> surrender. This is especially true of the antifilsal glands of keratinous fibers. 3s it was surprisingly found that. this l \ fachtei-Ie avoided \! e? <L & ~ n. can, if worked at a certain pH-3erd.ch without using an acid chloride using esters of dicarboxylic acids as starting materials.

he process for the coating of fiber-containing or

Substrates with a polymer is the best Invention dadurcli characterized in that a diamine and a Dicarboxylic acid ester in dilute form at a pH value between about 9 »5 and 11 in the presence of the substrate increased temperature and possibly non-use a catalyst reacted v / ground.

The substrates should expediently be in a cleaned form, so that the structure formed in the i * orm of a film

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BATH

layering on the substrate is as uniform as possible. The method according to the present invention is particularly suitable for woolen and woolen articles in all stages of processing. As already stated, we prefer: i as the exibstrate; Keratin-containing fibers or materials made therefrom are used because their properties are particularly improved after treatment according to the method of the present invention. The reaction is preferably carried out in an aqueous medium, optionally in an aqueous emulsion with a solution of the component, which may be insoluble in water, in another solvent. The consentrations are chosen so that a coating of the desired thickness results on the substrate. The thickness of the coating depends on the type of substrate, apart from the concentration of the aqueous solution or emulsion used. Absorbent substrates, which therefore absorb a certain amount of the aqueous solution or dispersion, are given a coating thickness even at lower concentrations that is only possible with higher concentrations in the case of non-absorbent substrates. The person skilled in the art can easily determine the optimal conditions for each substrate through experiments. In general, coatings with a weight of approximately 1-4 ^l ß>, preferably about 2-3 ^c / °, based on the dry weight of the coated substrate .n desired se '.

As starting products within the meaning of the invention are suitable

009843/1728

sor.dsrs aiiphatic diamines, such as those used in the manufacture of Polyamides (5Tylon) are common. for the coating of materials containing keratin, the The use of hexamethylenediamine is found to be particularly suitable, since a high anti-felting effect is achieved here. G-ute ila-free effects can also be achieved using e.g. I "hyiondiamine or trimethy! Hexamethylenediamine can be achieved. The abovementioned diamines are also particularly suitable because they are easily accessible industrially in large quantities are.

Dicarboxylic acid esters for the purposes of the present invention those which are derived from aliphatic (including cycloaliphatic) and aromatic carboxylic acids. Examples of aliphax Carboxylic acids are sebacic acid, cork acid, adipic acid, succinic acid, dodecanedicarboxylic acid, pimelic acid. Of the cycloaliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, for example, is suitable. from The aromatic carboxylic acids have in particular terephthalic acid, isophthalic acid or a mixture of ! Terephthalic acid and isophthalic acid proved to be beneficial, a mixture of 70 parts by weight of isophthalic acid ester and 30 parts by weight is particularly suitable Is terephthalic acid ester. The esters of terephthalic acid and isophthalic acid are preferred, inter alia, because they are easily accessible industrially. For example, falls a mixture of bis-phenyl terephthalate and Isopthalic acid bia-phenyl ester in the above proportions

- 6 -. - ^ ■ j / Hjr * 00984 3/1721 BADORlGtWAL '"

halts nisson as a large-scale product that can be used for the purposes of the invention without further processing. In general, the 3is-I? Heiiylester of dicarboxylic acids are preferred for the purposes of the invention, because they are relatively easily accessible and have a favorable reactivity for the reaction with the diaicin at temperatures of about 80-90 ⁰ C, provided the reaction is in the presence of Catalysts is carried out.

If ^ esters of aliphatic dicarboxylic acids as starting • products are used, especially those suitable which, owing to their low melting point at temperatures below etv / a 80 ⁰ O emulsify easily in water or can be solved.

Esters of dicarboxylic acids with lower aliphatic alcohols are less suitable for the purposes of the invention because they only react very poorly with the diamines, even in the presence of a catalyst, at the temperatures, which are portable with regard to the substrates to be coated.

"Activated dicarboxylic acid esters" react particularly easily with the diamines without the use of catalysts requirement.

The term “activated dicarboxylic acid esters” includes those in the sense of R. Schwyzer, B. Iselin and M. Peuver (HeIv. Ohim. Acta £ 8 (1955) 69) understood. The active

Vieruiig takes place through electron-attracting groups, whereby aas Garbcnyi-Xohlenstoifatom positive and one nucleophilic attack by amino groups more accessible jui-iacht will. The I ^ achteii of these connections, however, lies in that they are relatively expensive and not available on an industrial scale. A particular advantage of the The present invention is accordingly that not only such "activated" dicarboxylic acid esters can be used can, but that "at the specified pH range and below Use of catalysts also those esters can be used as starting materials that are not "activated" in the sense of the above. Versions and technical T are available.

According to the invention, the reaction between the initial constituents on the substrate is carried out at a pH between approximately 9 and 11, preferably between approximately 10.2 and 10. Carrying out the reaction at a pH of about 10.3 has proven to be particularly suitable. This applies in the first place when a keratiiilialtige ^ aser, preferably full, is used as substrate. At this pH value, the anti-fungal effect achieved is optimal; on the other hand, the extent of damage to the whole is kept so low that it is practically of no importance. The pli-fourth is adjusted to the stated range by adding acid, aa the diamines used, for example the hexamethylenediamine and uric e bases. Particularly advantageous

09 8 4 3/1728 ^BAD

The use of glacial acetic acid is responsible. It has been found that glacial acetic acid also acts as a catalyst for the reaction. Particularly in cases, in which for obtaining a complete reaction at the applicable temperatures up to about 9O ⁰ C, a catalyst is required, is adjusted with glacial acetic acid to said pH. On the other hand, especially in those cases in which a catalyst is not required, such as when using activated esters, the pH can also be adjusted with other acids such as mineral acids.

It has already been stated above that the method according to the present invention can be applied to wool with particularly advantageous technical results. Combed pieces can be coated according to the method of the invention without loss of good spinnability. Sheet structures such as knitted and knitted fabrics as well as woven articles can also be coated properly according to the method of the invention. Streichgarnartikel are particularly easy to handle, a cleaning operation are subjected during worsted articles useful, for example by isoionic wash at 70 ⁰ C. The same is true when using the method according to the invention on finished products such as garments (sweaters, socks and the like.). The coating of wool according to the invention leads to extremely felt-resistant products, ie the coated wool can be subjected to the maintenance operations required during use without this

Ö.Q & BtäA 17 28 bad

entanglement or shrinkage of the material in an undesirable manner Extent occurs. The handle of the "treated articles" is excellent.

As has already been stated, bisacetic acid is particularly suitable as a catalyst. Good results were for example also achieved with imidazole and 1,2,4-triazole.

To carry out the reaction, ie the polycondensation, the mixture is heated to an elevated temperature. The upper limit of the temperature to be used depends primarily on the substrate to be coated. When using wool, temperatures of about 10O ⁰ C should not expediently be exceeded. The lower limit is determined by the flow rate of the components, possibly taking into account the catalyst. When coating wool, it is particularly expedient not to use "dry" heat, but to achieve the temperature increase so that the soaked substrate is brought into a steam atmosphere. It is easiest if, in this sense, temperatures of about 80-90 ° 0 are used, since these temperatures are obtained when the soaked whole is placed in a steam atmosphere at riormalpressure. No special equipment is then required other than those that are available in wool processing plants. Manufacturing industry dampers work at the temperatures mentioned, The duration of the heat treatment, - '"^' - 'A / cMij BADORiGiNAL _ το

008843/1720

especially the damping depends on the activity of the output components taking into account the eventual applied catalyst. To protect the wool, the steaming time should be about 10 Hin. do not exceed. on the other hand these steaming times are sufficient for an adequate anti-felting effect.

the size of the anti-shrink effect of wool, i.e. the The main effect of the anti-felting finish is the tightness

■ I responsible for the hygiene pad achieved. The]? Smile

■ The shrinkage of knitted wool is particularly low in wool treated according to the method according to the invention,
if a Hylon run of about 1-4 5 », preferably from
about 2-3 f °, based on the dry weight of the wool, is formed. Such a level is achieved with wool in that with a solution liquor which contains about 70-90 g of dicarboxylic acid ester per liter and about 150-200 pounds of diamine per liter, up to a liquid absorption of about 70-

^ 90 ^c / o of the dry wool weight soaked v / ird. In the case of other concentrations, the liquor uptake must be adjusted accordingly.

If the reaction components are not soluble in water are, the water-insoluble component can be dissolved in an inert organic solvent and this with the aqueous solution of the water-soluble component can be processed into an emulsion. The addition of an emulsifier a promotes the stability of the emulsion. The emulsion can then be adjusted to the desired pH value

008943/1728 bad owp «^

■ uiid ^ qsq'oQT ^ or if a catalyst is added. The shelf life of the emulsion depends on the reactivity of the components and the catalyst. Even at. Using "activated" dicarboxylic acid esters such as ihlokresylesters, 2,4,5-2-chlorophenyl esters, p-nitrophenyl esters and o-l-nitrophenyl esters, the shelf life at room temperature is about 2-3 days. In the case of less reactive esters, the shelf life is correspondingly higher. As solvents in the above sense, for example, p-xylene, benzene and carbon tetrachloride can be used.

After the Uylon layer has been produced, the treated Wash wool as soon as possible, preferably first with warm and then with cold water. If the Formation of the BTylon split off alcohol component of the dicarboxylic acid ester Is not soluble in water, can be washed with a solvent with which the mentioned Alcohol component can be removed more easily than with water. This is especially true for the ihLokresylester.

If the dicarboxylic acid esters used according to the invention are not known, they can be used according to known ones Methods, especially according to the so-called "mixed. Anhydride-Kexhöde" (Sh. Wieland and H. Bernhard, Liebigü Ann. Chen., 5_2 "_2_, 190 (1951); R.A. Boissonnas, HeIv. Chic :. Acta, 34, 874 (1951), J. R. Vaughan Jr. and R. L. Qsato, J. Amer. Chem. Soc, 74> 676- (1952); 2Y. P. Albert-

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son, Organic Eeactions, _1_2, p. 157;), the "Carbodiimide" method (J, 0 .. Sheehan and G- .P. Hess, J, Amer. Chem. Soc, 72? 1067 (1955) j the "acid chloride" method or according to other known processes-are produced.

The method according to the invention results in its application, on full to felt-free products that have not yet achieved a felt strength in terms of the obtained felt strength have a good grip 'that differs from untreated wool practically indistinguishable. Such an effect

P is particularly considering the work that are carried out in numerous countries in this technical field, extremely surprising. The through the Treatment caused minor damage to the wool compared to the prior art methods extremely low. A particular advantage of the process of the invention is that it is continuous on an industrial scale can be carried out as a single bath process with the above-mentioned effects. This single bath process can be used in

^ the continuous ones customary in the wool processing industry Dyeing machines are carried out, the padding only instead of the. Staining solution the impregnation solution contains according to the invention. The steam washing and drying zone can remain unchanged.

example U - -

17.5 mmol of bio-phenyl terephthalate are added in 30 ml Dissolved piperidine .. 70 mmol of hexamethylenediamine and 1.6 g of Emulphor 0 are dissolved in 50 ml of water. The two

00984371721 " ¹⁵ "

Solutions are mixed with vibration to obtain an emulsion. The emulsion is made up to 100 ml with water. This emulsion is used to impregnate a woolen knitted fabric of 20 × 20 cm and a weight of 25 g with a cover factor of 4.0 and up. squeezed to a weight absorption of 70-80 ^σ / ο, based on the dry weight of the wool. The treated wool samples are a) steamed at 90 ⁰ C for one hour and heated b) at 100 ° 0 for one hour. It was then washed with water and dried. The samples were then subjected to the washing machine test, which is described in Z. sat. Textile ind. 66 , (1964) 358; cf. also H .'- J. Fleuning, Melliand Textilher. 44 (1963) 189, 288. The result after 15, 30, 60 and 120 minutes of washing time is shown in Table 1 below

-.are reproduced. The specified numerical values_ / the percentage Area shrinkage based on the original area.

Table 1

15th Min. 30th Min. 60 Min. 90 Min. 120 min. Washing time a; 3, , 6 7, 2 13, 3 19th »5 23.4 ο) 6, 11 6th 17, 2 24 , 9 32.5

From the table above it can be seen that we get a better result with steaming than with dry heating

Example2: ·.

70 mHoi hexamethylenediamine and 1.6 g Emulphor 0 are in 50 ml of water with the addition of the one indicated in Table 2

001043/1731

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added amount imidazole "dissolved. 17.5 mmol Terephthalsäürebis-phenyl ester are at 5O ⁰ C in 50 dissolved in the specified solvent of Table 2 ml. Diese'beiden solutions are combined under vibration to form an emulsion" is made. Using this emulsion an equal wool knitted fabric at 5O ⁰ O is impregnated and then steamed for 20 min. At 80 ⁰ G. The results of the washing machine test are given in Table 2 below.

Table 2

■ Solvent catalyst 15 min. 30 min. 60 min. 90XIr ... 120M. P-xylene 5 ^ imidazole -2.7 -0.4 -0.8 2.1 5.4

Tetrachloro- 5 $ imidazole 0 0.7 0.7 3.8 6.2 carbon

Example 3:

20 g of hexamethylenediamine and 1.5 g of Emulphor 0 and 1.25 g of imidazole are dissolved in 50 ml of water. 5 g of bisphenyl terephthalate are dissolved in 50 ml of pJ-xylene or carbon tetrachloride. Both solutions are processed into an emulsion as described in Examples 1 and 2. This emulsion was used to impregnate woolen knitted fabrics as used in the previous examples. In some cases, woolen knitted fabric extracted with ethanol was used (cf. the information in Table 3). The impregnated wool knitted fabrics were subjected to a steaming process at 8O ⁰ G. The corresponding times are given in Table 3. The then washed and

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triumphed "besohictiteten ßegftriQlE.e were cfem ublio & en WaseliAasoMiieiitest tntei'wori'eM .. In addition, control gest'j? iele ai-eeem WasolimasoiiiaeAt lmtiworfeRjüimsis iiiob with" eirter Besoeem were made. (Cf. the -erste », - 4" ropes of the 9} a "belle 3) * .Di © results of the ^: " -v / asetoasolii33.en.t © s * fes siixd ixi of SaTaeile 3. -

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0098A3 / 1728

Table 3

Ali "HBL solvent steaming time 15 min. 30 min. 60 min. 90 min. 120 min. 36 i» (min)

16.9 39.0 only ethanol
extracted
untreated - 19.9
29.1 38.9
45.6 45.7
56.6 61.7
63.2 65
65 , 0
,8th 1
< 17.5 26.7 only ethanol
extracted 10 15.2 30.9 47.3 54.7 58 , 5 15.5 24.1 only ethanol
extracted 20th 16.6 30.0 47.0 54.0 58 , 0 19.0 2.5 p-xylene 20th -2.7 -0.4 -0.8 2.1 5 , 4 14.8 3.1 η 15th 1.7 2.5 4.7 8.7 10 , 5 T6.1 4.2 Il 10 1.7 3.6 5.0 8, ϊ 10 , 7 15.4 4.7 Il 5 0.8 5.0 7.3 13.5 18th , 9 - - Tetrachloro- ι
carbon ι ; 20th 0 0.7 0.7 3.8 6th , 2 CO
O
O
CJ - 15, 2.2 3.5 7.2 11.5 13th ,1 - - 10 1.3 4.4 8.7 12.1 17th , 3 - - 1.5 6.0 12.8 23.1 25th ,1

In the above table, "AL" means the alkali solubility of the wool. This was determined according to the method of M. Harris and A. Smith - in accordance with the IWY regulation. / "Amer. Dyestuff Reptr., 25., 542 (1936), see also" Specifications for Test Methods "; International Wool Association, Technical Committee, published by the Internat. Woolsecretariat, London (196.0) ^

The abbreviation ¹¹ HBI "means the urea bisulfite

Solubility determined by the method of K. Lees and] ?.] ?. Els- A _< krarde / ^

value determine iVT ^ i ^ oG Int. ¥ ool text. Res. Conf.

Australia, YoI. C, 363 (1955) ^ 7

The following can be seen from the results shown in the table: The alkali solubility iii all. Pallen unchanged. The HBL is among the coated ones Wool knitted extremely low. This indicates very severe Wo11 damage, i.e. those treated in this way Wool knitted fabrics are practically useless. The reason here- -

for is that not according to the invention applicable pH-Werc was worked. The example 3 is therefore only a comparative experiment that shows that although at other pH values than those required according to the invention, an anti-felting effect is achieved which But wool damage is so great that a technically usable product is not obtained,] for technically usable products Products, the HBL word must be at least around 10.

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808 843 / $ 17!

Examples 1 and 2 are only intended to show that a better result is obtained with steaming than with tempering and the different solvents are used. However, even according to Examples 1 and 2 was not worked at the claimed pH values, i.e. with regard to ■ the wool damage, the results are not γ sufficient.

Example 4:

5g of a mixture of 30 parts by weight terephthalic

. bis-phenyl acid ester and 70 parts by weight isophthalic acid bis-phenyl ester are dissolved in 50 ml of xylene. The amount of glacial acetic acid given in Table 4 and 20 g

Hexamethylenediamine is dissolved together with 1.5 g of Emulphor 0 in 50 ml of water. The two solutions are processed at 50 ⁰ G under vibration into an emulsion. Mi τ; This emulsion is impregnated with wool, as was used in the previous examples. the

.Imprägnierung carried out at 50 ⁰ C. The mixture is then pressed to a moisture content of 80-90%. The thus-impregnated wool fabric is steamed at 8O ⁰ C. The steaming times are given in Table 4. It is then carefully washed first with warm and then with cold water and the knitted fabric is air-dried. the

Results of the washing machine test are in Table 4 specified.

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09843/1728

In rc? - 19 - 4th 30 min. 60 min. 1619003 120 min. 10 Tabel 16.3 20.2 27.0 Glacial acetic acid 20th time 15 children 11 ', 5 15.9 90 min. 21.9 " 10 10 11.7 13.6 23.7 23.0 34.0 10 20th 9.7 13.5 19.5 20.5 29.5 15th 10 11.0 22.3 35.4 29.1 51.8 15th 20th 9.2 25.3 41.8. 24.3 54.7 20th 11.0 47.5 20th 10.3. 51.1

The handle of the fully knitted fabrics treated in this way is excellent. The HBL values are around 10 «

Example 5;

7.3 g of bis-thiocresyl sebacate (referred to as "thio" in Table 5) or 9.5 g of bis-trichlorophenyl sebacate (referred to as "tri" in Table 5) were dissolved in 15 μl of benzene each time iö ^ g hexamethylenediamine, 8.4 g glacial acetic acid and 1.5 g Emulphor 0 are dissolved in 80 ml water. As in the preceding examples, 2 emulsions were prepared from the last-mentioned solution and the respective ester solutions. Wool knitted fabrics were impregnated at 5 ⁰ C and steamed at 8O ⁰ C. The results are shown in Table 5.

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Ester Steaming time
(MLn.) untreated Tabel 5 30 min. 60 min. 90 min. 120 min. Gys 2 AL HBL 0 9.5 PA un
soluble 1 1 attempt thio 5 Ethanol 10
extracted 15 minutes. 5.4 7.5 19.6 13.2 10, 0 14, 3 5.0 19 1 a thio 5
(without ice
vinegar) Ethanol 20
extracted • 2.0 0.8 8.1 10.5 13.4 8th, 0 14, 5 2.8 42, 9 b thio 15th 0.8 5.9 " 6.8 9.3 10.8 8th, 7th 11 2 4.0 34, 4th G thio , ¹⁵
(without ice
vinegar}'/ ' 3.1 -1.9 2.6 5.9 8.8 13, 82, ι
S. ά tri 5
(without ice
vinegar) -2.9 -1.0 0.5 5.9 13.0 f e tri 5 -2.5 3 9 39 f 45.6 56.6 63.2 65.8 10, 16, 5 26, 0 18, H 29.1 30.9 47.3. 54.7 58.5 - 17, 5 24, 7 - ⁱ 15.2 30.0 47.0 54.0 58.0 - 15, 1 - k 16.6

CD CD O CO

In the table above, "Cys" denotes the gy content that was determined in wool hydrolyzates according to the instructions of T. Gerthsen "^! Technical Committee of the International Wool Association, Oslo, report no also Rapport. Er. 16, Paris

The value "PA insoluble" refers to the "performic acid - ammonia solubility". This xirird according to the method of

-i

Peter Alexander. (Biochem, 7.5 £ 177 | j952 |) determined.

The following can be seen from Table 5: With a steaming time of five minutes when using the method according to the invention (test a), an excellent felt-free effect is achieved, with very little wool damage. This results from the fact that the cystine content and the performic acid-ammonia-insolubility properties are unchanged compared to untreated film (test h). The HBL value for wool treated according to the invention is the permissible value of 9.5 · The alkali solubility remains unchanged compared to untreated wool. Test b corresponds to Experiment a, only working without the amount of glacial acetic acid given above, ie the pH value claimed according to the invention was not adhered to. This experiment shows that the PA insolubility value increased considerably, the HBL value fell below a reasonable value and the cystine content was also humiliated,

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008843/172 »

d. H. Considerable damage to the wool has occurred, affecting the "treated products for technical use" to make something useless.

Experiment G shows that "if the dipping times are too long, also with Application of the method according to the invention a Wollschädiguri £ can occur. The optimal steaming times can be achieved through simple experiments can be determined easily. Experiment d shows that at pH values outside the claimed range still ' a considerably stronger wage damage occurs.

Example 6:

Equipment of Carded crocheted: 7.3 gr.Sebacinsäurebis-thiocresylester in 15 * £ - dissolved benzene. 16.2 g of hexamethylenediamine, 8.4 g of glacial acetic acid and 1.5 g of Emulphor are dissolved in 80 ml of water. At 5 C, both solutions are processed into an emulsion while vibrating. Woolen knitted fabrics are impregnated at 5 ° C and steamed at 80 ° C for five minutes. The results of the washing machine test are shown in Table "6 below.

Table 6

-O 15 ' -rO η ' 6o 5 9o ' 12o t according to the invention: 12th ,1 25th , 2 2, 2 6.8 12, O untreated , 5 , 2 58 45, o 49, 6th

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009843/1728

The table shows that a good felt-free effect is achieved. The handle of the so "treated carded yarn is excellent and taking into account the fungus-free effect achieved unsurpassed.

Example 7
Combing equipment:

The amount of the ester mentioned in Table 7 (Abbreviations as in Table 5) is dissolved in 15 parts of benzene. 15 S-hexamethylenediamine, 1.5 g-Emulphor O and - if given in Table 7 below - glacial acetic acid is dissolved in 80 ml of water. These solutions are at 5G, like described in the other examples, processed into an emulsion. This emulsion is used to impregnate a woolen sliver and steamed for 90 minutes at 90 ° C. Then it will be fine washed with water and dried. The results of the washing machine test are given in Table 7. The specified V / ies relate to the size shrinkage.

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BATHROOM OBlGINAJ.

009843/1728

1611003

OHH O

VD OJ v- , V- UA O UA : ο CO CO KA CO KA V- " O UA D- OJ V KA op. OJ OJ 4- OJ UA VD Ό VD D-. VD KA CO σ> CO - UA CVJ OJ KA VD UA OJ O ! OJ OJ rs O UA O UA KA D- D- UA OJ OJ OJ KA VD UA O V OJ O KN CO CO KA OJ UA VD UA KA OJ, .. VD OJ KA KA OJ O V VD D- C ^ O OJ cT> D- OJ OJ KA CT> UA O KA OJ O OJ OJ V OJ D- O OJ KA V " O CT> co V O OJ O UA KA OJ O OJ OJ VD D- VD D- VD CO r> V rs D- O KA OO VD UA V D- CO OJ OJ O V " V " V O v " UA OJ O VD C ^ D- V V OJ O OJ O V O V V CO ₁ V O KA V O v " he" vD ~ D ^ OJ V OJ O - · Η O •H •H O O • r4 U U £ _ | -P •H •H , Cj -P -P CD ■ , d +3 -P UA -P. UA UA ω -P LTA Ldel UA LT \ UA he" W. i I «rl D- UA C2 CO O • H CO O D- co O

009843 / 1.728

The! Table shows that "when using Glacial acetic acid (pH value at the claimed level) compared to the comparison searches without glacial acetic acid (pH value above 11) improved shrinkage resistance is achieved. The handle of the Goods treated according to the invention are excellent.

Example 6:

This example shows that at pH values outside the claimed An inadequate anti-felting effect is achieved in the area.

7.5 o ^r · sebacic acid bis-p-thiocresyl ester are dissolved in 15 2il 3enzene. 20 g of hexamethylenediamine and 1.5 g of Emulphor® dissolved in 80 ml of water. With glacial acetic acid it is added to the ⁴ in

the pH value given in Table 8 is set. Be at 5 ° C these solutions as described in the other examples processed into an emulsion. Wool knitted fabrics are soaked and steamed. Details as well as the results of the washing machine test are given in Table 8.

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009843/1729

φ H H Q)

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009843/1728

According to the invention, wool combs "had a excellent grip *

Example.9; -. "

This example illustrates the dependency of the felt-free effect on the pH of the impregnation solution, It shows that at a pH of Ίο, 5 under the conditions given in this example opti- ~ nal effects are achieved * while "at higher. or lower pH values the "felt-free" effect is worse. dDer-Grlff der "Treated goods were in particular in the optimal pfr range of 1o, 5> excellent.

5 g of bis-phenyl ester of te ^) are ground in 50 ml of p-xylene solved. 20 g of eexamethylenediamine and 1.5 g of Emulphor 0 are used dissolved in 50 ml of water. The pH is adjusted by adding Glacial acetic acid adjusted to the values given in the table. An emulsion is formed from these solutions at 5o C while vibrating made with which wool tops are impregnated. The impregnated Combs are dampened at 8o G. The steaming times, Further details and the results of the washing machine test are given in Table 9.

- 28 -

009843/1728

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009843/178

Claims (14)

Patent claims 1. Process for coating fiber-containing or thread-like substrates mit_einem polymers, characterized in that a diamine and a dicarboxylic acid ester in dilute! Form "at a pH value between about 9 ₅ 5 and 11 in the presence of the substrate at elevated temperature and optionally reacted using a catalyst. 2. The method according to claim 1, characterized in that the Diamine is hexamethylenediamine. 3. The method according to claims 1 to 2, characterized in that that the dicarboxylic acid ester is a bis-phenyl ester and an aliphatic one or aromatic dicarboxylic acid. ".... 4. The method according to claims 1 to 3, characterized in that
that the dicarboxylic acid ester is terephthalic acid-bis-phenyl ester
and / or isophthalic acid bis-phenyl ester. 2. Process according to Claims 1 to 4, characterized in that that glacial acetic acid is used as a catalyst. 6, method according to claims 1 "Ms 4 ·, characterized in, that imidazole is used as a catalyst. 7 _# Method according to Claims 1 to 6, characterized in that respectively. Acetic acid. ,
the pH value is adjusted by adding glacial acetic acid / * 8. The method according to claims. 1 to 7? characterized in that the pH is adjusted to about 1o, 2 to 1o, 6, preferably about 1o, 3 wine 9 ·. Process according to claims 1 to 8, characterized in that that the reaction takes place in a water vapor atmosphere at temperatures from about 8o ° C to 9o ° C. 10. The method according to claims 1 to 9 »characterized in that that the substrate is a keratin-containing fiber. 11. The method according to claims 1 to 1o, characterized in that that the substrate is wool. 12. The method according to claims 1 to 11, characterized in that the reaction in an aqueous medium, optionally in Carried out in the presence of an inert organic solvent will. 13. Ancestors according to claims 1 to 12, thereby gekennaelehnet, that the substrate has all of the reaction components containing solution or emulsion is soaked and then heated. 14. Vafahren according to claims 1 to Ip _5, characterized in that the substrate washed after completion of the reaction, and. is dried. pn " 009843 / Hgp