DE1419118A1 - Process for improving the properties of polyamides - Google Patents

Description

Patent attorney 141011ft DR.-ING. WALTER ABITZ. ¹ ^ ¹ * ¹ ' ^ö

Munich

July 2, 1957 HB-451

E. I. DU POHT DE HEMOUHS AHD COMPAHY 10th and Market Streets, Wilmington 98, Delaware "V" St * A "

Method for improving the properties

of polyamides

The invention relates to a method of modification of polyamides.,

The invention aims to develop a process for the production of shaped structures made from synthetic polyamides are formed, to which unsaturated organic acids, preferably the salts thereof, are chemically bonded. Another object of the invention is to produce molded articles from a modified polyamide according to a novel Process in which unsaturated organic acids are chemically bonded to the polyamide.

In the additional patent application P of July 1, 1957

to the parent patent, ........ (patent application P 16 008 IVc / 8k) is a novel type of polyamide comprising these polymers and shaped structures, which are characterized by the presence of acid groups which are attached to the

_BA O

Polyamide bound or grafted onto this. This grafting or binding can e.g. B. take place, however, «to the Polyamides irradiated while they are in contact with unsaturated monomers containing acid groups.

It has now been found that such polyamides and in particular shaped structures such as fibers, threads, fabrics or films that contain such modified polyamides, can be produced by a penetration of the polyamide or the molded article containing the same with a polymerizable acidic vinyl compound, preferably acrylic or methacrylic acid and uniformly excites polymerization in the entire penetration area by the polyamide or the molded structure containing the same is subjected to polymerization conditions, for example heated to a temperature that induces addition polymerization able to excite, preferably to a temperature of at least 60 °. If desired, a polymerization agent can be used and optionally also a polymerization inhibitor be present to facilitate the polymerization. Although the use of the polymerization agent and the Polymerization inhibitor on the polyamide or the shaped structure can be carried out separately, they are usually applied advantageously together with the polymerizable acidic vinyl compound on the polymeric material, e.g. B. in the form of a mixture, making sure that the mixture is kept at a sufficiently low temperature to excite the polymerization during the application of the

809805/0744

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To prevent mixture <,

The properties of the polyamides or of the structures containing the same can be further improved by the acid-modified polyamides into a salt, preferably the calcium, ammonium, potassium or sodium salt. Satisfactory results are often obtained by applying the polymerizable vinyl compounds to the polyamide or applying the structure containing the same in such a way that they are completely penetrated; on the other hand, it often can it may be desirable to treat shaped structures in such a way that penetration is directed and only part of the structure, e.g. its surface layers, the polymerizable vinyl compound included., This amendment of the procedure permitted the achievement of very good effects ■

. & in detail in the additional patent ... ... (patent application

P «of July 1, 1957} are special

good properties obtained when the total number of acid groups in the modified polyamide more than 300 per 1000 kg of the polyamide.

According to the invention, the properties of shaped structures made of polyanides, such as yarns, fibers, fabrics, films, Flakes and the like, improved by treating the molded article with a polymerizable acidic vinyl monomer or mixtures thereof under non-polymerizing conditions, I is, as described in detail later, the

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desired penetration is achieved. Thereupon the acid is both polymerized and on that which it permeates Polyamide grafted, d. H. chemically bound to the same by working in the penetration area evenly a polymerization is excited. This uniform polymerization excitation is, as described later, by thermal Effect causes. It has been found that uneven polymerization excitation leads to mere surface effects leads through which the valuable products obtainable according to the invention are not obtained.

After the unsaturated organic acid on the shaped Is grafted structure, a salt of this acid can be formed, and any salt is suitable, such as Amine, metal salt or ammonium salt. The salts are after the principles of behavior of ion exchange resins as set out in 0. H. Osborn, "Synthetic Ion Exchangers", MacMillan Publishing Co., 1956 '.

In the drawings shows

1 shows a graph of the relationship between the concentration of an ammonium persulfate pathogen (plotted on the abscissa) and the amount by weight of acrylic acid grafted onto the hylon (plotted on the ordinate) at low pathogen concentrations and under relatively mild polymerization conditions (the curve is in detail in Example 5 discussed),

80 98 0 5/07 AA BAD LOCAL

FIG. 2 shows, in a group of curves, the same relationship as FIG. 1 at different acid concentrations and proportionally higher pathogen concentrations (these curves are discussed in detail in example 6),

3 shows a schematic representation of a method suitable for continuous implementation of the method according to the invention Device (which is described in detail in Example 10) and

4 to 6 photomicrographs at approximately 50X magnification of the cross-section of threads obtained according to Example 10, namely, FIG. 4 shows a true and complete penetration of the thread cross-section by the dye, FIG. 5 an approximately 30-fold true penetration of the dye into the thread and FIG. 6 shows an untreated control sample in which there is essentially no washable penetration of the dye into the thread.

Unless otherwise stated, a nylon fabric "66 ⁿ " is used in the examples, a taffeta fabric which is woven from a yarn of endless €; n polyhexamethylene adipamide threads of 70 denier and a titer of 2.0 denier per thread. The polyamide is made of hexamethylenediamine and adipic acid (hence "66") and has a relative viscosity (defined in US Pat. No. 2,385,890) of 37 »39 equivalents at -NH ₂ end groups and 92 equivalents at -000H end groups ^{: y} 10 g per 10 g of polymer (hereinafter referred to as "39 amine end groups" or "92 carboxyl end groups"). The polymer. ^ Wlr-ä ^ after the use of 0.34 mol $ acetic acid (the end groups of which are naturally

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lent are not titratable) produced as a stabilizer, what 15 amine end groups is equivalent. From these values, the method of G. B. Taylor and J. E. Waltz is used to calculate "Analytical Chemistry", Volume 19, 1942, page 448, the number average molecular weight to about 13 700.

The "standard washing" to which the samples are subjected takes place in a 20-1 wash machine by immersing them for 30 minutes in 18.1 water at 70 ° which contains 0.5 $ detergent. The detergent is sold under the type designation "Tide" by the Proctor and Gamble Company, Cincinatti, Ohio, V.St.A » used in, means brought to market «It contains except the active ingredient well over $ 50 (sodium) phosphates (Chemical Industries, JSO, 942, July 1947). The detergent has approximately the following analytical composition:

Sodium Lauryl Sulphate 16

Alkyl alcohol sulfate 6

Sodium polyphosphate 30

Sodium pyrophosphate 17

Sodium silicates and

Sodium sulfate 31

The tendency of the fabric to become electrostatically charged (static propensity) is given as the direct current resistance measured in ohms at 25 »6 ° in an atmosphere of (unless otherwise stated) 50% relative humidity; 'co · high values indicate the tendency to accept and retain a static charge; they are given as a logarithm to the base 10 and labeled ^{"log R 11} _{" or similar}

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The following quantitative information for hole melting is determined by allowing heated glass beads of constant weight and diameter to fall from a certain height from an oven at constant temperature onto the fabric ο-The temperature at which a stain appears on the fabric than the first damage temperature and the temperature at which the glass bead through melts completely through the tissue than the hole melting temperature Marked in the following qualitative information of tendency to Iiochdurchschmelzen relates to "poor" to about 300 °, "detrimentally alter ¹¹ to about 400 to 500 °, "good" to about 600 ° or a little more and "excellent" to noticeably above 600 ° ο The fiber melting temperature given in some examples is determined by connecting a thread, which is taken from a fabric if necessary, to an electrical heated drill and reads the drilling temperature, at which a visible smell oil or immediate decomposition occurs.

The deformability is determined by bringing a yarn sample into contact with a drill heated to about 225 °. A thread which, in contact with the drill, can be stretched to 2 to 3 times its original length »without the individual threads melting, is called" elastic *, and if the stretching is maintained during cooling, it is called "post-deformable * _O

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The wrinkle recovery is determined by taking a Crumples up the fabric of Hanä and watched the speed, with eggs it will recover from this treatment. the Wet wrinkle recovery is the speed with which which the wrinkles disappear from the crumpled tissue, when it is moistened. Numerical values are obtained using the Monsanto Crease Recovery Method described in ASTM test standard D 1295-53T (American Society for Testing Materials Manual). The compositions given in the following examples are unless otherwise stated, expressed in percent by weight.

The following examples serve to illustrate the invention, without in any way exhaustively identifying it.

Example 1

4 pieces of nylon fabric "66" made of a 34-ply yarn of 40 denier we3. * Den placed in a polyethylene bag, which is charged with a polymerizable ^ mixture of an unsaturated acid; is, containing the ammonium persulfate from an aqueous solution is 30 cm, the 2'j # acrylic acid and fo as pathogens 0.2. The bag is sealed and the polymerizable mixture is allowed to penetrate the prayer at room temperature for 30 minutes. The bag is then heated to 90 ° to effect the graft polymerization. Compartment removal from the dfiin bag have the <every "ou eise" visible polyacrylic acid! Coating, o & r in 5 SpUIa ^ kJLen / Eämlich ?. <, -

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for 1 hour agitation in distilled water at 60 °, is removed, these samples show that by grafting the acid on the nylon the weight of the fabric and the carbox, 7lendgruppen have increased and that after By forming the salt of the acid, the fabric has a lower tendency to pick up a static charge, and a higher resistance to blow-through melts than the untreated material own ;! ι

Sample A is used for the above 6 rinsing cycles in one Soxhlet extracted with water for 12 hours. The increase in weight ■ amounts to 7 »9 #> after the end of the treatment.

Sample B is titrated for its carboxyl groups; it contains 937 carboxyl equivalents / 10 g of polymer, while the original Kylongewsbe has 92 carboxyl end groups.

Sample C is treated with a 1, above solution of sodium hydroxide in distilled water. "After thorough rinsing, log R (at 50% relative humidity) is 8.0 compared to 13.3 for an untreated control sample. The sample is bad S'3hr high wet wrinkle recovery. By 5-Stawdard Was3hungen with the detergent "fide" · anschlieBsendes and rinse using tap water IFE Ioi is replaced by Ca. The sample then has a higher resistance to hole melting and a dry grit *.? «..... ·:.

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Sample D is agitated at 60 in an aqueous solution of 0.3 $> calcium acetate in three successive cycles of 30 min each. The end product has a high resistance to hole melting. It is now subjected to 20 standard washes using the detergent "Tide" in tap water the resistance to hole melting remains unchanged. After the calcium acetate treatment, a piece of the 34-pade yarn taken from sample D has a breaking strength of 337 g at an elongation of $ 26.4> A similar piece of yarn made from an untreated fabric has a breaking strength of 348 g when elongated $ 0. This shows that the method according to the invention does not adversely affect the breaking strength of the nylon.

A t s ρ i el 2. ■■. - ■ i (is-i ^: · "^ ·

The method according to the invention is suitable for treatment

• ν, · .- · :, - 'j. - ^: ·. ■■■■ '"■ · ■ -'-- τ.; - ^. - ■ of films. Filae are also particularly suitable for explaining the effect of the method according to the invention on the high temperature resistance;

Two pieces of nylon film (11.4 x 7 * 6 cm 0.05 mm) are placed in '^; treated the impregnation and polymerisation stages according to Example 1 with an acrylic acid-ammonium persulphate solution. After treatment, the sample E is in a Soxhlet. 42 - extracted "'h' with water, sample P as described above for the P _r obe D • lestilliertem rinsed in water at 60 ° and treated ml'c calcium Both film pieces to a placed heated metal block and covered with a glass plate

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covered. None of the pieces melt or stick to the glass plate ₉ when the temperature is raised to 300 °. In contrast, unmodified film of nylon "66 ·" melts at 264 °. It is observed that upon cooling to room temperature the calcium acetate treated film retains the same flexibility as the initial untreated material, while the non-metal ion treated sample E eats brittle and decomposed and breaks into pieces when bent.

Example 3

Two pieces of nylon taffeta 17.8 χ 22.9 cm (samples α and H), which are woven from a 34-thread polyhexamethylene adipamide yarn of 70 denier, together with 40 cm of a polymerizable mixture of 10 $ freshly distilled acrylic acid, 0.05 ^ ammonium bipersulfate x (as excitation), and 89.95 i> water in a polyethylene bag of 5 cm 25.4 3O _P introduced, the bag wire with pressure sensitive adhesive tape (ü? ype Scotch) closed to prevent the outflow of the liquid, and then 30 min stored at room temperature to allow the liquid to penetrate a polyamide structure. It is then * introduced for 1 hour in a held to 90 ° forced air oven to cause the graft polymerization. "The polyamide samples are rinsed after removal from the bag with distilled water of 60 ° and ansehliessend 15 hours. Ir Ernest Soxhlet extracted with water. Both Samples show a weight gain of about $ _{19-20 o}

Sample H is agitated for about 1 hour in distilled water containing 1 Ji of sodium carbonate. After rinsing and drying, their log R is 7.8 compared to 13.3 for an untreated control sample. It is then agitated for about 1 hour in an aqueous solution containing 1 % calcium acetate, whereby the Na ion is replaced by Ca ion. The sample modified in this way has a pas melting temperature of 455 ° compared to 233 ° for an untreated control sample *

A weighed portion of sample G is dissolved in a solution of 100 parts by weight of methanol, 27 parts of lithium chloride and 1 part Formaldehyde dissolved. The dissolved sample is titrated potentiometrically with methanolic sodium hydroxide solution - it contains 2130 Equivalent carboxyl groups (hereinafter referred to as 2130 carboxyl end groups labeled) 10 g of polyamide each.

Ha is water-soluble polyacrylic acid _f can be shown that the CarboxylgrujDpen be bound by the inventive process chemically bonded to the polyamide structure. To do this, the acid-grafted polyamide is dissolved in a solvent and then water is added in order to precipitate the polyamide again (and to dissolve all polyacrylic acid that might be in the solution). To illustrate this, a second portion of sample 6 is dissolved in 90% formic acid, the solution is filtered and the modified polyamide is precipitated again by adding water. The precipitated polymer is filtered off, the precipitate is washed 8 times with distilled water and then placed in a vacuum oven from 20 to 70 °

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dried. Analysis of the precipitation by the technique described above reveals the presence of x ^r on 2158 carboxyl end groups. This shows that the acrylic acid is grafted onto the polyamide through a previous bond, because polyacrylic acid is water-soluble.

A third portion of sample B is dyed together with an untreated control sample in a liquor containing a basic dye. The aqueous dyeing liquor containing (based on the weight of the fabric) 2 ° / o p-amino ^ phenaeyl-trimethylammoniuiachiorid ,, the diazetiert and niethy to li-.beta.-cyanoethyl-M ^! Aniline is coupled "as well as 2 $ fatty alcohol sulfate as wetting agents" The ratio of fabric to liquor is 1:50. The samples are kept free for 1 hour at 100 ° in the liquor. Sample G much deeper colors (orange) than the non-treated control sample (yellow) _e Me microscopic examination of the cross section of genommeren from Sample G filaments aeigt that are the same uniformly colored through and through, d. fa. every single thread is completely made of acrylic acid before the graft polymerization.

B.Ü..J s j> ie 1 4

The presence of a pathogen supports the acceleration of the polyasrisation stage, but is for the ■ invention

gcüftäaöe procedure not essential % . ·. ·: -. · .---

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=> 15 -

Two pieces (samples I and J) of the nylon fabric described in Example 1 are soaked in separate 40 cm portions of an aqueous solution of 15 ° freshly distilled acrylic acid. Impregnation and polymerization are carried out according to the technique of Example 3, with the exception that the samples are heated to 90 for 2 and 48 hours to induce polymerization. After washing the compartment for five times in distilled water at 60 °, no noticeable weight increase was found in sample I, while the weight increase in sample J due to the grafting of acrylic acid was $ 13.9. Analysis of part of sample J shows the presence of 1220 titratable carboxyl end groups.If another part of sample J is dissolved in 90% formic acid, then precipitated again by adding water and then washed repeatedly, the washed precipitate gives analytically 1289 carboxyls ~ end groups, which proves the chemical bond of the acrylic acid chains to the polyamide molecule. -

This example explains the effect of a 'change in the pathogen concentration on the amount of acrylic acid', '' which "is grafted onto the Efyion at a certain heat temperature and time ο

A series of 8 nylon samples (K to R) is injured in polymerizable masses which contain 15 1 ° freshly distilled acrylic acid and ammonium persulfate as pathogens in the amounts given in Table 1. One works according to

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Example 3 and soak for 30 minutes at room temperature and heat each sample individually for 20 minutes to a temperature of 90 °. To Once the reaction has taken place, parts of each sample are rinsed with hot water distilled water and determines the weight gain (Table I).

sample Addition of ammonium Weight gain persulfate, io the Pasern, $ __ K 0.0 no I. 0.01 no Iff 0.02 5.5 N 0.03 14.7 * 0 0.04 17.4 P. 0.05 17.9 Q 0.10 11.7 R. 0.2 11.9

Pig. 1 shows in the form of a graphic representation the relationship between the increase in weight of the tissue due to grafted acrylic acid (plotted as the ordinate) and the pathogen concentrate: ion (plotted as the abscissa). The values obtained show that the relationship between weight gain and catalyst concentration has a maximum value at about 0.04 to 0.05 $ ammonium persulfate. Without restricting the present invention in any way by this explanation, it is assumed that a minor component of the polymerizable composition acts as an inhibitor and prevents grafting at such low exciter concentrations. ' If the action time is extended, the grafting is done writes described even oirae Brreger additive.

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This example illustrates the effect of changes in the acrylic acid concentration in a range of pathogen concentrations on the amount of acid that can be used under certain conditions is grafted onto nylon.

A series of 16 nylon samples, QA through QP, are soaked in the polymerizable compositions shown in Table II. To the Penetration of the nylon, the samples are soaked for 30 minutes and then the temperature of each sample over the course of about 15 seconds increased to 100 °, with polymerization taking place. the Samples are held at 100 ° for 6 min, then removed, cooled and rinsed repeatedly in distilled water, whereupon their weight gain is determined (Table II). The results obtained are graphically shown in Fig. 2, which shows the relationship between the weight of the nylon grafted acrylic acid and the concentration of ammonium persulfate at different acrylic acid concentrations of the Treatment solution shows. The top curve corresponds to one 25 ^ igen aqueous aerylic acid solution, the ones below Curves correspond from top to bottom to concentrations of 20, 15 and 10 $ "

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Table II

sample Ammonium per.sulf a t, Acrylic acid, Weight gain Gffwebes, fo QA 0.05 10 12.6 QB 0.1 10 9.1 QC 0.2 10 7.3 QD 0.4 10 5.6 QB 0.05 15th 16.0 QW 0.1 15th 13.3 QG 0.2 15th 10.0 QH 0.4 15th 8.3 QI 0.05 20th 21.2 -QJ 0.1 20th 16.9 QK 0.2 20th 14.0 QL 0.4 20th 11.3 QM 0.05 25th 24.6 QIT 0.1 25th 21.2 QO 0.2 25th 17.2 QP 0.4 25th 13.6 By S- ρ i e 1 7

The application and implementation of the polymerization at ver-IiältniBEiässi ^ j high temperature has the advantage that you _s ~ £ o lymerisat :. Since it has been reduced, the polymerization can be carried out in the presence of inhibitors and the Hass wrinkle resistance of the fabrics is improved.

A piece of nylon fabric sample is RA, 30 min in a 25 $ strength Isösung of freshly distilled methacrylic acid and 0 ₉ 2% AüiinoaiuiQpar & ulfst impregnated. The piece is wrapped in aluminum foil in the wet state obtained by the impregnation.

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and then ironed for 2 minutes with a tailor's iron heated to 125 °. After rinsing and drying, the weight gain of the sample is 40.5 # If this experiment is repeated with the exception that the polymerizable mass containing persulfate contains 0.025 $ hydroquinone (a common polymeric cation inhibitor), the weight gain of this sample is RB despite the presence of the inhibitor $ 10.8>.

When the above experiment with a fresh nylon sample RC using let a polymerizable is repeated, the i> acrylic acid, 0.025% contains 25 of the methyl ether of hydroquinone as inhibitor and 0.2 fo ammonium persulfate, the weight gain is 14 "2 $,

This experiment is repeated with a tissue sample after the RD employed in \ sample RO technology with the exception that prior to ironing x more than half of which it decided 'r .'-' wetting liquid (40 $ flüssigkeitsaufnähme based on ,: ^: the original fabric weight) removed by wringing out »Despite the lower amount of acrylic acid available for grafting onto the nylon surface, a weight increase of 12.3 #» ■ is obtained

When you get this? Test with a P _r obe RS repeated except that the ironing time is reduced to 1 min, bsträgt weight gain $ 11.6 "-

Sine Probe RF becomes the same treatment used in Probe RD subject to the exception that the "polymerization by immersion for 2 minutes in a kept at 115 to 125 °

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Silicone oil with the type designation DC 200 (from Dow-Corning Corp., Midland, Mich., V.St.A. brought on the market) will. After rinsing twice in chloroform, 5 successive washes in the detergent "Tide", Rinsing in dilute acetic acid (to remove nations) and rinsing twice with distilled water is the same Weight gain $ 12.9 «

A sample RG is treated like the sample RE, with a Wood's metal bath being used instead of the silicone oil, which is heated to 110 to 120 °; the weight gain is 12.2 ^.

Da inhibited asrylic and methacrylic acids grafted onto nylon can be done by taking the grafting reaction at temperatures in the region of 120 to 125 °, the costly and dangerous distillative removal of inhibitors becomes avoided from the unsaturated acid "

Example 8

The door of any polymerization initiator used is not critical. This example explains the use of an "organic pathogen in the grafting of acrylic acid onto nylon"

A Hylon sample S is drunk in a polytaerizable aqueous mixture, since it contains 25 $> freshly distilled acrylic acid and 0 * 5 £ a * a ~ A «odii8obutyroamidin-bydrQehloriä» After penetration of the NyXoss uuroh 50%! ÜrMrskuag becomes

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the tissue wetted with the solution in a polyethylene bag enclosed and heated in an oven for 60 minutes at 60 ° and then for 30 minutes at 90 °. After rinsing three times in distilled Water at 60 ° is the sample in two cycles of 10 and 120 minutes at an initial temperature of 60 ° each time with a 0.3 $ aqueous calcium acetate solution reacted and then Stirred for 30 min in distilled water at 60 ° The increase in weight of the sample treated in this way is 3.9 #, which is an average of 290 carboxyl end groups / 10 g of polyamide is equivalent to.

Example 9

This example illustrates the application of the method according to the invention to polycaproamide, i. H. 6 nylon.

A sample T of 6-nylon taffeta made from endless threads is soaked for 30 minutes in a polymerizable mixture containing 25 $ aqueous commercially available (ie inhibited) acrylic acid and 0.2 $ ammonium persulfate. The P _r obe is then removed from the solution and wrapped in dripping-wet state in aluminum foil. It is then ironed in this envelope for 2 minutes at a temperature of 115 to 125 °. After five times washing the sample in distilled water at 60 ° using a Rührwäschers, wherein one each time 10 _s rain washes the weight gain is by the grafting of acrylic acid 17.9 #. On repeating the experiment with a second sample a weight gain of 19 $ _f 2> is obtained "=

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If sample T is as in Example 1 with a liatrium ion containing Solution is treated »is log E 8.7; she owns high absorbency and extraordinarily high Wet wrinkle recovery. If you look at them like sample D Treated in Example 1 with Caleiuma acetate solution, it shows excellent resistance to Loehdurei ice cream and its melting temperature is 234 (for an untreated Control sample) increased to 518 °.

The method according to the invention is described above for intermittent implementation, but can very easily be carried out continuously using a running film or strand of yarn. A suitable device for this continuous implementation is shown schematically in FIG acrylic acid having a content of 0.2 $> Anmioniumpersulfat) containing De »s yarn 2 is then by means of guide rollers 11 ~" 12 and 13 in the Sefäss 9 "out the geschmolsene Woodsdhes metal contains 10 of a temperature of 120 °. in The acrylic acid is grafted onto the nylon thread under the action of heat and the pathogen in this vessel the yarn is guided through the bath 14 by guide rollers 16 to 22. In this bath, the treated yarn

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the polymer sitting on the surface was washed off. The product is then fed from the guide 24 to the pack 23 via the guide roller 25. The acid-modified polyamide yarn obtained can then be used as described above for the purpose of forming the? Salt form are treated with suitable positively charged ions.,

Example 10 -

In the device according to Mg. 3, a nylon thread of 840 denier is treated, which is supplied from a pack 1. Since »Vessel 4 contains the polymerizable mass, the composition of which is given in Table III, Vessel 9 contains Woöd's metal, which is kept at a temperature of 120 °, and Vessel 14 contains distilled water heated to 90 °. The speed at which the yarn is guided through the individual vessels is given in the table; The total contact time for each container is calculated from this speed and the distance of the yarn in each container. The sample U only comes with the polymer-readable mixture. rend of the Hindu passage through vessel 4 in contact * the sample Y on the other hand is in the polymerizable ?! The solution is pre-soaked for about 1 hour before it is passed through the system. With these exceptions, the treatment conditions are the same for each P-obe

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Table III

Sample Aqueous Hand- Garage- Total- Aufüfrouf-

! .BungalBaung dizzy- * PääSn «q- she times

Äeryl ^ excitation speed, m / min ^ ?? ™ ^{ßS tent} ° ^ee acid

ü " $ 50> 0.5 fo 8.05 3 ₉ 8 see 3.8

Peracetic acid

V 25 $ 0 _p 2 Si 5.12 1 hour 6.0

Ammonium persulfate

After the acid grafting, the carboxyl content of the samples is determined analytically, they are dyed in the basic dye liquor according to Example 3, and the depth of the grafting, which gives an indication of the depth of the acrylic acid grafting, is then determined at their transverse step. A portion of each sample is boiled at a yarn bath ratio of 1: 100 in a solution containing 0.5 g sodium carbonate / g sylon. This forms the sodium salt of acrylic acid, whereupon the log ß and laser melt temperature of the product obtained are determined. Similar determinations are carried out with a piece of a control yarn W which is treated in the same way as the above test yarns, but is not guided through the device according to FIG. 3.

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Table IV

sample Acrylic acid form recording
at basi
shear color ~
material Cross Sodium salt form Fused fiber
temperature, -COOH-
analysis Fig. 5
Figo 4
Fig. 6 cut log R 316
360
236 ü
V
W. 200
571
51 deeper,
colored
ter hung
same-
moderate
no
coloring 9.8.
8.8
13.3

These results show that the sample V, which was sufficiently impregnated long in the acrylic acid solution in order to obtain a complete penetration _s is modified over the entire cross-section and as the sodium salt high antistatic properties and Faserschmelzbestäm 'has accuracy. Due to the short-term contact with the polymerizing compound, the TJ sample is only modified on the surface, to a depth of perhaps 30 $> the Faeerradius. This modification is sufficient to achieve substantial antistatic properties and an improved fiber melt temperature when the sodium salt is formed. It should be noted, the analysis dasi a smaller number of aa carboxyl groups as && ώ above preferred minimum value (300) yields, Eber dieae analysis includes dea niehtmodifizierten Fadenkcm as well as the highly modified "coat" or "ring *. Bach de» erfiaöungegsu & i & ea method Kau »Thus modifying the" skin "of a barrel:? © rdss,« βόη ζ. Β.

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to achieve a reduced water absorption and / or improved adhesion a modification going through the entire fiber is undesirable "

Example 11

A piece of a fabric made of 6-6 nylon weighing 1.8 g is, after about 3 minutes' injuries, heated in 2 enr of a 25% solution of freshly distilled acrylic acid in benzene in a loosely plugged reagent tube on a steam bath for 10 minutes. The testicle is left to stand overnight, washed in distilled water, then neutralized with dilute sodium hydroxide solution and washed again, the drying rate is 29 $ 5, the sewing fabric has shrunk during the treatment. '

this experiment is repeated with the exception that υ; üie Acryleäurekosaseatratiosa the Behandlungsiöaungen to about 1S fo reduced j is the weight gain # 7. Me Älkalisalae each of these products has a good resistance to isochromic penetration and just as good antistatic properties

Wiiia is & above all this ysrsueh repeated with the exception that ri.'ir .: Rphiisöß trad the Stsiiealassea over take place on an open spare glass _{v there} is no selectable increase in weight of the

i 8sts »3tellea _u jiae BagreBsusig des. Luftsatri-tts Pt-oi'6 aehfeiiit therefore promote the grafting ku f · - ■

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men *

Suitable polyamides for carrying out the invention Process sinl those synthetic linear polyamides, which from polymerizable Monöaminöcarbonsäüren or their amide-forming derivatives or from suitable diamine and suitable dicarboxylic acids or from amide-forming derivatives of these compounds are obtained. Polyamides »in which the intrasacid ataid groups do not consist of * are finally aromatic in nature, d. H. where in to each re-leaching unit of the polymer molecule an alipaatisehe -HCH- group is located. The -R- group can be hydrogen, halogen, a monovalent organic Eest, Aifeylen or dargleiehen. Typical polyamides of these Art are z “3. from an aliphatic diamine and a aliphatic acid and contain the recurrences unit

»Χ» Z - Y - Z - _t

where »X- and -Y- divalent aliphatic or syeloaliphatic Represent groups and -Z- the group

OH

η «

- -. -cT- ■. ■ · ■■ "• ■ '■' ^i: '"^:; - ■ ·

means. Olympic examples are polyhexamethylene adipamide and polyeaproaiiiid (ie Bylon 66 bawo 6) _e Other suitable polyamides have the repeating structure

where -A- is a divalent aromatic radical \ mä

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-X- and -Z- have the same meaning. An example of this Polymers is polyhexamethylene terephthalamide. Besides that polyamides can be used that have repeating units such as

-A-Z-B-Z-

_X-Z-B-Z-

wherein -B- is a divalent alkaryl (such as xylylene). Another class of suitable polyamides which contain repeating units other than aromatic intric acid amide are the polymers obtained from piperazine, such as piperazine and adipic acid, piperazine and terephthalic acid and the like copolyamides, condensation copolymers in which the amide bond is the predominant bond, and polyamide mixtures are also suitable. As stated earlier, in order to achieve the structures according to the invention, these polyamides have a high molecular weight (ie they are fiber-forming and their surface is not tacky at room temperature). As described in US Pat. No. 2,071,253, polyamides should have a number average molecular weight of at least about 10,000 (relative viscosity 24) in order to be fiber-forming Il 130 948 described.

Under ⁿ shaped "s structure" is here in any Haumtsmperatur spatially fixed "shape to understand. B may be, for example, an _e barrels, a film or a Häutchea © _t EIA woven, knitted or EIU

809805/0744 _ba0

Mushroom, a bristle or artificial straw. The structure can also be in the form of a flake, powder, or fine particle have that achieved after grafting a certain band object can be reshaped · The spatial form has for the treatment with the stipulation no critical importance that structures of greater thickness proportionately stricter conditions “d, h. require longer soaking time, prints or the like in order to achieve a satisfactory To obtain distribution of the polymerizable mass in the molded polyamide structure.

The molded structures made of polyamide, onto which the unsaturated acid is grafted according to the process according to the invention, are characterized by a large number of pendent acid groups which are chemically bonded to the polymer chain. Such pendant acid groups are, as described in the American patent application Serial So. 595-210, accessible for titration. In order to obtain the advantages that can be achieved according to the invention, aan binds in an area in which a modification is desired _f . Usually sufficient unsaturated acid _{f in} order to obtain at least about 300 equivalents of such titratable acid groups per 10 ° g of polymer (based on the modified range). Bless acid groups are composed of the total number of all free acid end groups derived from the polymer and also the groups derived from the grafted organic acid.

809805/07 kk BAP ORIGINAL

"Polymerizable acidic yinyl compound" is to be understood as meaning any homopolymerizable organic acid (and / or the anhydride) which is able to form a metal = ·, amine = * © of the ammonium salt and at least one reactive unsaturated group such as vinylene or aoetylene group contains. Since the acid should penetrate into the formed structure and low molecular weight acids penetrate the formed structure more easily, acids with up to 5 carbon atoms are preferred. However, even with more acids, for _e B, 20 or more carbon atoms in the chain suitable, although less good. For maximum activation, it is desired, that the double bond near the acid group is "seems figuration Such Koi also the speed raised stabili" hen ₉ with which the acid in the molded body penetrates "Suitable unsaturated monocarboxylic acids are ss. B. Acrylic -., Methaeryl-, crotonic, Furanearbon- and propiolic acids homopolymerizable bifunctional unsaturated acids (ζ · Β <> itaconic or fumaric acid) are equally well suited _ö Besides the acids are also derivatives "such as acid chlorides, acid anhydrides, and Säurehalbester Säurehalbamide effective ,, Any unsaturated organic compound is suitable which contains functional groups that can be converted into the acid form by hydrolyzing (ζ ,, Β. Esters, nitriles, amides) oxidizing (eg "B <» aldehydes or ketones) or others The unsaturated * acid can also contain substituents whose binding to the polymer may be desired in order to give it a different purpose en au give, such as greater static reduction, moisture repellency, colorability ₉

809805 / 07ΑΛ

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Non-flammability, etc. These substituents can also be introduced by copolymerizing suitable monomers with the unsaturated acid.

In practicing the present invention, although homopolymerizable unsaturated acids are preferred, but also mispolymerizable unsaturated acids (a. B, maleic acid, Chloromaleic acid, etc.) can be used in the polymerizable mass, if in combination a suitable one Yinylmonomsres is present »with which the acid can form copolymers.

In addition to the unsaturated carboxylic acids, which are a preferred class of compounds, other acids can also be used. Examples of these are the sulfonic acids (see B ₀ styrenesulfonic acid, ethylene sulfonic acid), unsaturated alkyl or aralkyl acid phosphates, phosphites, phosphonates and phosphinates * Acid alkyl sulfates and carbonates with unsaturated carbon-carbon bonds are also suitable *

The use of mixed unsaturated acids as well penetration and grafting with an acid and subsequent Penetration and grafting with another Acids are evidently variations of the procedure which are of a technical nature.

Because the polyamide before the uniform polymerization excitation with a polymerizable acidic vinyl compound is penetrated, extends the "modification of the formed structure at least over a substantial part

809805/0744

^JU BAD ORIGINAL

of the body of the final product * Usually the one that is shaped Polyamide coated with the acid or padded on as a dispersion, solution, pure liquid or emulsion. For Liquids are suitable for spraying, the polymer counter = stand can also be immersed in the liquid. The acid can also be supplied in vapor form, preferably the molded polyamide is dipped into a polymerizable one Solution containing mass «,

The penetration then becomes an affinity of the polyamide easier for unsaturated acid «If you treat nylon fabric with aerylic acid solution and remove excess liquid mechanically, much more remains Acid returned in the wetted nylon than expected. By mechanical removal of the fluid from the excitation of the Polymerization is thus increased because the effectiveness the acid loss is reduced by homopolymerization of the acid © excess outside the filaments.

An acceleration of the penetration is promoted by longer contact time and movement the temperature at which the polymerization is excited), with excess pressure or in the presence of swelling agents, dye carriers or the like. Smaller amounts of Wetting agents, surface-active compounds and the like are also suitable for achieving more effective penetration »

80980 5/0744

If desired, the penetration of the polymerizable Restricting mass to a zone close to the fiber surface can do so by reducing the contact time or temperature (before polymerisation), use of acids with a larger chain position or use of unsaturated ones Acid in a lower concentration. If the acidic vinyl is applied from a solution, water provides that preferred solvents. Other inert liquids, such as alcohol, benzene, toluene, high-boiling ethers and the like, however, are also suitable for this purpose.

While zweckraässig penetrates the molded polyamide structure with the polymerizable acidic vinyl compound in normal application, it is also the vinyl a solution of the Pölyami & it enforce _a From the mixture obtained, the shaped structures then by the customary processes, such as wet or Brockenspianen or pouring, are obtained * The uniform excitation of the graft polymerization can take place before, after or during the deformation <,

The use of sines chemical Polymerisationserregers Although, _r as shown in the examples not _f essential for the inventive method trotsdem but can be such an agent verv / end when it is applied in sufficient amount to to a uniform polymerization throughout the penetrated body allow ». Without thereby limiting the present invention in any way, it is assumed that; s eiae inconsistent ü-iToh Aur-iVin: ycn.z sissa eh; »! - ί r-.oren 3r-re»; ers on the

8098 0 5/07 AA BADORiGiNAl.

Surface of a structure penetrated with acid »leads to a" skin formation "which inhibits the polymerisation of the deeper acid. Thus, if in the inventive method, a chemical excitation is used, bringing it under niehtpolymerisierenden conditions in admixture with the acidic vinyl on _β As described in the examples, the use of a chemical agent is often advantageous thermal since then the Polymerisationserregung sharp with less Conditions is possible and the acidic vinyl can be applied in the presence of a polymerization inhibitor.

A large number of conventional free-radical-forming pathogens can be used. Examples of these are the peroxy compounds, i. ho the -QO- group containing compounds, e.g. B _e Diacylperoxide- such as diacetyl Peroxyeäurea as Peraiiieisensäure or peracetic acid _P Bibutyrylperoisyd _β Bipropiany1peroxyά, dibenzoyl peroxide and Üialkylperoxyde like dimethyl, Biäthyl- and Bipropyiperexyde or _a persalts such as ammonium uad alkali metal persulfates, perborates and -perearbona te, etc. Examples of other usable _P free © Badikal-forming pathogens are the Asine »z. 3 _O p _e nzalazin, Diphenylketazin etc. ,, and the Azoerreger as a "a 'Az © diisobutyr0ami ·" Dim. The water-soluble pathogens are preferred because it is desirable to dissolve them together with the unsaturated organic acid

preferred.

05 / ^ 7 ^ 4. BATH

As the examples show, a low concentration of pathogen increases the effectiveness of the grafting and is therefore preferred. In addition, with high concentrations of pathogen (e.g. 1 to 2 $> ammonium persulphate) there is a tendency for the nylon to turn yellow, which makes it unsuitable for some purposes, _etc. Therefore, if a pathogen such as ammonium persulfate _{P is} added, concentrations of about 0.005 to 0.5 $ _{P are} recommended, with 0 _p 01 to Q, 2 $ "being preferred." Of course, the method according to the invention can, as described above, with good results in the presence of limited amount of oxygen from the air can be carried out without the addition of other pathogens »

Ee is usually desirable to heat the polymerizable composition in contact with the polyamide quickly to the Polymerisationsteisperatur, whereby the graft efficiency is increased and the Säureverli t is reduced _o The temperature in the polymerization stage is usually about 60 ° or more, "The upper limit is determined AU3 the volatility or decomposition temperature of the unsaturated Säureο When using acids of good heat resistance, it may be desirable that Polymerisationsseit by carrying out heating under pressure to verkürzenΌ Before "· preferably not the temperature is greater than about 200 ° _f '* ena acrylic acid, or about 250 ° if methacrylic acid is used. Higher temperatures are more suitable for achieving a good wrinkle resistance recovery. Lower temperatures during the polymerization excitation can be used if the contact time is increased.

80980 5/0744 bad original

HD-451. .

such as room temperature, are suitable for certain combinations of acid vinyl, chemical agent and the like.

In general, it is desirable to graft a sufficient amount of unsaturated acid onto the polymeric body to obtain at least 200 titratable acid groups per 10 g of the polymer, preferably at least about 300 such groups Properties of the substrate achieved. Amounts to titratable to about 1000 acid groups are suitable for polyamides that are to be post formable, while still larger quantities are desired of titratable acid groups for superior heat resistance "The mechanism is formed after which this intermediate _s is not entirely clear. (Theoretically, one could penetrate the unsaturated organic acid in the polyamide substrate and chemically bonded to reactive sites of the polyamide "," chemically bonded "is meant such bonding by chemical rather than purely physical bonding forces (such _o as absorption) that the unsaturated acid can be obtained by extraction with solvents for the sur acid modification acid used not be removed "Further still, as shown in the examples, the concentration t bound to the polyamide terminal carboxyl groups even substantially unchanged when the polyamide is dissolved and reprecipitated from a medium was _f in which the polyvinyl acid alone is soluble. The process according to the invention is therefore more than the simple one

809805/0744

Application of a coating, paint or finish to the fiber surface shows that "Initial activation is likely to occur at or near the amine end groups normally found in the polyamide" Much less grafting occurs when the polymer has a low concentration of amine end groups (z ₀ B. 5 equivalents of Arainendgruppen / 10 g polymer) or the amine end groups are destroyed by bleaching with peracetic acid before the unsaturated acid acts. Theoretically, it is assumed that once the polymerization of the unsaturated acid at or near the amine end groups is excited? the acid chains grow according to the mechanism of normal vinyl polymerisation «Additional excitation points are formed at other points along the polyamide molecule by breaking the chain of the growing acid chains. The binding of the unsaturated acid makes the polyamide highly receptive to basic® dyes» Cross-sections of acid-treated graft-modified nylon fibers = den * those dyed with basic dyes _P tend to have a deep j color that goes through the entire fiber, which proves that the acid has penetrated the fiber «

If the test conditions. be adjusted so that complete penetration occurs _s results dia mikroDkopische examination of the cross section of the dyed yarn a clearly defined Hing, the clear depth of Sindringimg sseigt "For some purposes, a solcäe beg :? en κ te liißfe'ingimg er-ο Z. Eo ka "iR sxoh due to" a high Feuehti ^ koltfi · -

809805 / 074Λ BAD 0 _RIG , _NAL

Restraint over the entire cross-section with the sodium salt of acrylic acid modified nylon cold or clammy to the touch »This is sufficient for fabrics» that must be resistant to radiant heat »For body clothing, however, it is usually desirable to limit the penetration to about 10 $ (measured along the fiber radius ) or in some cases even .Less as 5? 6, to avoid restricting to a "cold" handle "in the zone of penetration of the carboxyl terminal group is at least about 300/10 g polymer ₀ in

partial penetration, the indication "10" g polymer "refers only to the lin & ring zone _p not to the non-penetrated core. Results obtained by analyzing the entire thread must therefore be corrected for the respective content of the penetrated and non-penetrated constituents in the fiber, which is determined by measurements The cross-section of the dyed threads can be determined. In general, the number of carboxyl end groups grafted onto a nylon sample and the weight resulting from the grafting is directly proportional to the sample / 1Q g has, after a prose & fcualsn weight increase of about 3 »0 about 439 end groups to o values of about 1100 and 2000 end groups correspond to percentage weight increases, of about 9 _S & or» 22 ₉ 3 »

Ia the last stage of the process, i. the formation of the salt of the acid, the positive ions apparently charge themselves to the Ca'feoxyXgruppsn of the acid, which was previously added to the Uylon.

809805/0744

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was grafted »and thus form an ionic lattice structure» which gives the polyamide the unusual and unexpected properties described. Many of these properties are characteristic of crosslinked polyamides "Substantially insoluble" Unlike the usual crosslinked polyamides *, however, these polyamides according to the invention remain essentially soluble in 90% formic acid or has been subjected to polyamide polymerization in the presence of polyfunctional acids or amines or exposed to extremely high levels of radiation. "As already described, any salt can be formed by simple treatment in aqueous solution." acid-modified polymers very easily absorbed. If two or more cations are present in the treatment solution, "one ion is usually taken up preferentially over the other" If, for example, both sodium and calcium ions are present, the calcium sala is formed in preference to the sodium salt "This can be easily directed by _f treats the säiireräodifizierte polymers with a solution comprising a Oalciumionenab · = · • separator (for ₀ example sodium hexametaphosphate) containing Under these treatment conditions, the l ^ atriumion preferably commenced before the calcium ion If the sodium cation is replaced with lithium _p obtained similar hydrophilic and v? ärraefe ~

809805 / O7ΑΛ

- 38 - ORIGINAL BATHROOM

strength properties. Sometimes you may want that to treat acid-modified polymers simultaneously or sequentially with more than one ion species in order to produce multiple effects achieve »The calcium ion causes z. B. a very effective improvement in heat resistance. So you can after incorporation this ion into the body of a shaped structure on or near the surface (using a calcium separator and from Na ion) sodium ions bind to the anti = to improve static properties.

As examples of the metal salts that are suitable for the process according to the invention? Sodium carbonate, potassium carbonate, potassium acetate, calcium acetate, manganese (II) acetate, zinc acetate, copper (II) acetate, cobalt (II) acetate, ghroiu (III) acetate and the like may be mentioned. Phosphate grip strength detergent _s as the "Tide ^11, and even some hard Y / asserarten suitable as cation donors'

The dissociation constant of the acrylic acid grafted onto the polyamide is 5.6 χ ICf · '(Heilbron, Dictionary of Organic Compounds, Volume I, Oxford University Press, New York * 1953, Page 29). If one tries the salt of the acid-modified Forming polyamides with a solution containing an anion of much greater acid strength than the modifying acid is the development of the resistance to hole piercing very much low Good results achieved if. Metal salts with weaker acid anions than those of the modifying acid

809805/0744 BATHROOM

be used. When the strength of the grafted acid and those of the anion of the treatment salt are approximately the same, salt formation is facilitated by using the ion exchange resin © the usual way the concentration of the treatment salt is increased »

Good resistance to hole melting is achieved if the acrylic acid-modified form of the polyamide is exposed to sodium hydroxide solution. However, if you "the sodium replaced by sodium chloride does not improve the resistance to hole melting results have been shown to _p that the calcium ion on a molar basis more effectively improve the melt stability than the sodium ο results while alkali metal ions such as lia-ion * preferred if an improvement in the antistatic properties is also desired. Further, while with acrylic acid plus metal ion modified Polyaiaidproben he NachV malleable aind _s if about 400 or more acid groups are introduced, the samples at the introduction of higher Konsentrationen of deriving from acrylic acid carboxyl groups (a ', above about 1000) are no longer naehverform = bar ο _m

Organic cations are suitable for forming the salt of the acid-modified polyamide. Any desired amine or quaternary ammonium compound can be used. Examples of these are ammonia, aliphatic: Lse _t aromatic ρ cycloaliphatic and he- 'terocycliseho JUsine, v? Ie Xthylamin, lf * in _r aniline, Be ^ rJ ^ -si ': i? i _r VyolQh.exylamxix _f

809805/07 UU BAD ORIGINAL

Piperidine, morpholine and the like. So is the nature of the quaternary ammonium ions used for salt formation are not critical. Methylpyriäiniumchlorido Trimethylbenzylammoniumehlorid, Tetramethylamraonium chloride and the like can fin = use the.

For the shaped structures according to the invention in the form of fabrics , the improved resistance to hole melting is primarily described above. In addition to these properties, such fabrics have an increased resistance to radiant heat and a higher resistance temperature; when heated to temperatures above their melting point _s dropwise neither molten polymer from nor do they stick to surfaces on adjacent. As shown, the polyamides at high temperatures have (z. B. "above 185 °) high elasticity WAM deformability <> Due to this deformability the geeäss the invention treated polyamide fabric (eg. Bo in the salt form) can, at high temperatures (. B. by deforming or forcing) into three-dimensional shapes and keep this shape after cooling o They assume the shape ₉ without the soap threads melting and without the handle of the fabric being adversely affected, if the fabric is again above about 185 ° is heated, it essentially returns to its original shape _o Yarns made from the salt form of the acid-modified polyamide can be stretched (drawn) at temperatures of 185 ° or more *.

80 980 5/07-U BAD

When a shaped structure (such as fiber or fabric), which is produced from the salt form of the acid-modified polymer according to the invention, is heated in the relaxed state to temperatures of 185 ° or more, shrinkage of 50 % or more occurs. This shrinkage is in addition to that which eliminated previous Bath deformations. Structural effects can also be achieved when yarns made of modified and unmodified polymers are combined in the same fabric or when the unsaturated acid or the positive ions are in a pattern (i.e., unevenly). be applied.

In addition, ordinary drawn polyamide yarn is treated in the manner described at elevated temperatures (e.g. above 185 °) compared to the untreated yarn highly stretchable.

The advantages obtained by the method according to the invention were largely described in terms of the effect on the polymer properties at elevated temperatures. The method according to the invention can, however, also give other very important changes to the tissue properties, for example tissue which unsaturated acid grafted ISTJ, from which then the sodium salt was formed a _v (30 to 40 i> improved) new crease resistance recovery at high relative humidity. Thus, the fabrics treated according to the invention, which have been wrinkled during use,

809805/0744 ^BAD original

can be restored to their original wrinkle-free state by simply dampening them and hanging them up to dry. Ironing is not necessary.

The polymer bodies treated according to the invention can of course contain the usual amounts of matting agents, antioxidants and the like, giving them a better appearance, obtain better light fastness, heat resistance and the like.

_BA0

809805 / 07Ai

Claims (1)

Patent claims ο processes for improving the properties of polyamides, in particular in the form of shaped structures, such as fibers, threads, fabrics or films, characterized in that one Penetration of the polymer or the shaped structure with a polymerizable acidic vinyl compound, preferably Acrylic or methacrylic acid, causes and in the penetration = zone uniformly stimulates a polymerization by applying the polymer or formed structure to polymerization conditions subjected, for example heated to a temperature capable of causing addition polymerization, preferably a temperature of at least 60 ° " The method according to claim 1, characterized in that one works in the presence of a polymerization agent and, if desired, a polymerization inhibitor *, Method according to claim 2 _r characterized in that one brings the polymerization initiator and optionally a polymerization inhibitor = sierbaren to the polymeric material together with the polymerized = acidic vinyl compound to act. Method according to one of claims 1 to 3 in "in the fact that the acid-modified polyamide or" molded body in the form of a salt, preferably the calcium · = "= ammonium · ο potassium or Natriurasala üfcerführt" 805/0744 ^{BAD ORIG} 'NAL 5ο Method according to one of claims 1 to 4, characterized in that that one directs the penetration of the formed structure in such a way that only part of it is polymerizable Contains vinyl compound. 6. Polyamide or molded structure containing the same, thereby characterized in that it is produced according to one of claims 1 to 5. BATH ORIGINAL. 809805/0744