FI60571B - SAETT ATT FAESTA KOPPARSALTER VID POLYAMID- ELLER POLYESTERPRODUKTER - Google Patents

Description

fuap> VI γβΙ «« Publication 60571 JSTa lBJ (11) UTLÄGGNINGSSKRIFT 0U0 '' ## (¾¾ C / ^ jv Patent Granted 10 02 1932

Patent meddelat (51) Kv.ik? /Int.ci.3 C 08 J 7/06, D 06 M 11/04 FINLAND - FINLAND (21) p »t * n« lh »k ·" 1 * '* - P «* nt» n $ eknlng 750267 (22) H »k * ml» p * lvl - Anaeknlngtdag 31-01.75 (23) Alkupllvft - Glltigh «t * d» g 31-01-75 (41) Become Public - Bllvlt offentllg 19-09-75

Patent · and register-held ..... . . ,. ,. .

_,. (44) Date of hearing: Jutkalsun pvm.— ^, _ 0,

Patent · och registrerttyrelten 7 AntMun utltgd och uttskrlfun publkerad 30.10.Ö1 (32) (33) (31) Pyritty etuoikeus — Begird prloritet l8. 03-71 *

France-France (FR) 7 ^ / 09381 (71) Rhone-Poulenc-Textile, 5 Avenue Percier, 75008 Paris, France-France (FR) (72) Andre Arsac, Vemaison, France-France (FR) (71 *) Oy Kolster Ab (5 ^) The way to attach copper salts to polyamide and polyester products - Sätt att fästa kopparsalter vid polyamid- eller polyesterprodukter

The object of the invention is to attach copper salts to polyamide and polyester 2 products by treating these products with hydrogen sulfide at a pressure of at least 2 kp / cm and then with an aqueous solution of the copper salt.

The invention is characterized in that before or during the treatment of the products with an aqueous solution of a water-soluble copper salt such as copper sulphate, the products are exposed to polyphenol.

FI patent publication 57 122 describes a way of attaching metal compounds to products of synthetic polymer in order to increase their electrical conductivity.

This known method is based on exposing the products to hydrogen sulfide under pressure, and then subjecting these articles to the action of an aqueous solution of a metal salt. This method is particularly suitable for the production of anti-static products, such as floor or wall coverings, and for the production of electrically conductive fabrics, such as heating surfaces.

60571

The products to be treated according to the invention are generally textile materials which may be in various forms, such as fibers, strands, continuous yarns, ropes or shaped articles, e.g. fabrics, knitwear, nonwovens or other materials containing them.

Kama textile materials are formed from synthetic polymers, such as polyamides (polyhexamethylene adipamide, polycaproamide), polyesters (ethylene glycol or propanediol polyterephthalate), polyamides of these or also aromatics of these types, including polyamide imides. alloys.

As described in the above-mentioned FI patent publication, the product is treated with a pressurized, hydrogen sulfide in the gas phase, for example in an autoclave under saturated steam pressure, after which the product is immersed in an aqueous solution of a copper salt such as copper sulphate at 15 ° C. be within 1/2 ... 2 hours.

According to the present invention, the copper salt treatment is carried out in the presence of a substance capable of swelling the treated material and forming bonds between this material and the metal components to be attached.

It has been found that polyphenols meet these conditions. Of the polyphenols which are well suited for carrying out the process according to the invention, mention may be made of orthodiphenol, methadiphenol and paradiphenol, 1,3,5-trihydroxybenzene or other polyphenol compounds such as tannins. The polyphenol can be incorporated into the product either by performing a polyphenol pretreatment prior to the hydrogen sulfide and copper salt treatment, or by adding the polyphenol to an aqueous solution of the copper salt such that the polyphenol concentration is at least 0.1% by weight, preferably 3 to 6% by weight. The product is then rinsed with water, the solution is drained off and the product is dried in any known suitable manner. It should be noted in this connection that the method can also be applied to silver salts, but in this case the results are less interesting, because the adhesion of silver salts fixed as described in the above-mentioned FI patent publication is generally good enough, and copper salts are preferred for economic reasons.

The weight of the product treated according to the invention generally increases by 2 to 10 #. This weight gain is due to the fact that the copper salts settle in continuous regular even surface layers, the thickness of which can be in the range of 0.01 to 0.5 depending on the treatment conditions. X-ray diffraction analyzes have shown that this deposit, i.e. the layer, is mainly cuprous sulfide. The adhesion of the precipitate is better than that obtained according to the above-mentioned FI patent publication, · and the same applies to the electrical conductivity and antistatic properties, which are very resistant to dyeing, washing, dry degreasing treatments, etc.

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The textile product treated according to the invention can be used as it is, but in most cases it is used as a component in untreated textile products such as floor or wall coverings, garments, etc., to improve these antistatic properties or to give them such good electrical conductivity as heating elements. The product according to the invention is then suitably added in the form of fibers, yarns or strands, e.g. also combined with other untreated yarns or ropes or made from knitted or crocheted fabrics together with other untreated yarns or threads.

The amount of material treated in accordance with the invention included in the composition of the untreated textile products may vary depending on the desired effect. In general, it has been found that an amount of at least 0.05% by weight already significantly improves the conductivity properties of the treated product and thus its antistatic properties.

The following examples illustrate the invention.

Example 1

Polyhexamethylene adipamide fibers with a thickness of 22 dtex (20 den), a length of 75 mm and pre-oriented are fed to an autoclave into which hydrogen sulphide is introduced under a pressure of 3 bar at 22 ° C. After one hour of treatment, the fibers are immersed in an aqueous solution of 60 ° C containing 5% by weight of copper sulphate and 5% by weight of methadiphenol, followed by rinsing under running water and drying in an oven at 60 ° C for 30 minutes. The weight gain caused by the treatment of the fibers is b, 2%. The electrical conductivity of the fibers is measured as follows:

The fiber is tensioned between electrodes spaced U cm under a bias voltage of 0.330 g, and a voltage of 20 volts from the battery is applied to the fiber. The intensity of the electric current flowing through the fiber is measured with a Galvano meter connected in series, and the resistance is calculated from the value obtained. The same measurement is then carried out after degreasing the fibers with trichlorethylene for a quarter of an hour at 50 °, and then drying the fibers in an oven at 60 ° C.

The following table shows the results of ten experiments with fibers treated under the same conditions, compared with those obtained with reference fibers treated with the same fibers under the same conditions, except that the aqueous solution of copper sulphate does not contain methadiphenol.

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Without degreasing After degreasing

O O

Reference sample 65-10 ohms 92.10 ohms

Methadiphenol-treated sample 2k.10 ohms 29-10 ohms

It is noted that fibers treated in the presence of methadiphenol have better electrical conductivity than fibers treated without methadiphenol and that after dry degreasing, the loss of conductivity is only 20% in fibers treated in the presence of methadiphenol, while its reduction is 1 + 0% in the second case, indicating that the copper salts have adhered more strongly to the fibers.

The surface of the treated fibers has a 0.2 μm thick copper salt coating. These fibers are added to polyhexamethylene adipan fibers having a thickness of 22 dtex (20 den) and a length of 75 mm when making a knitted nonwoven fabric. When used as a floor covering, the needled nonwoven product obtained is antistatic and remains so even after it has been cleaned several times with cleaning foam. This nonwoven product can also be used as a base for a tufted pile fabric.

The treatment has little effect on the dynamometric properties of the fibers. The treated fiber has a breaking strength of 83 g and an elongation of 5 * +% ·> while the reference fiber has a breaking strength of 73 g and an elongation of 58% · These measurements have been made with an Instron-type dynamometer.

Example 2

The "spunbonded" type, a nonwoven layer obtained by pressing continuous filaments, formed of continuous filaments of ethylene polyterephthalate with a thickness of 7.7 dtex (7 den) and a weight of layer 2 of 300 g / m, is placed in an autoclave fed to hydrogen sulphide at a pressure of 5 bar at 22 ° C. After one hour of treatment, the layer is immersed for one hour in an aqueous solution at 60 ° C containing 5% copper sulphate and 13% orthodiphenol.

The electrical conductivity of the layer is measured on a sample of 20 cm in length and 5 cm in width, without degreasing and after dry degreasing, under the same conditions as in Example 1. The results obtained are shown in the following table, which compares them with those obtained under the same conditions. identical layer, except that the aqueous solution of copper sulfate did not contain orthodiphenol.

Without degreasing After degreasing

Reference sample 62 ohms 200 ohms

Orthodiphenol treated sample 23 ohms 26 ohms 5 60571

It is noted that the conductivity of the treated layer in the presence of orthodiphenol is higher than that of the control layer, and that the decrease in conductivity after degreasing is smaller (13%, 223%, respectively), proving that copper salts adhere more strongly to the layer fibers.

This nonwoven textile layer is bonded by needling to another nonwoven spunbonded layer formed of continuous filaments with a thickness of 7.7 dtex (7 den) and a weight of 100 g / m, which is used as a heating wall covering. In addition to the heat and sound insulation capacity, it is stated that heat is generated evenly from the coating.

Example 3

Fibers similar to Example 1 are treated under the same conditions, except that methadiphenol is replaced by tannin powder "ALS, K, sold under the trade name Societe Transtanic.

The electrical conductivity of the fibers is measured in the same way as in Example 1, except that the measurements made after dry degreasing are replaced by measurements carried out after dyeing under the following conditions: - 0,1+ g of "Jaune Neopolaire 1+ GL" sold under the trade name CIBA -GEIGY, - 1 g of condensate of stearylamine and oleylamine and ethylene oxide, - acetic acid to adjust the pH to H, - water to a total weight of 1000 g

The ratio of material to bath is 1 g of treated material and 100 g of bath.

The fibers are then washed with cold water and dried for one hour at 60 ° C.

The results obtained are shown in the following table, and for comparison, the results obtained with the reference fibers treated under the same conditions are shown, except that the aqueous solution of copper sulfate does not contain said ?. tannin powder.

Without staining After staining

Reference sample 65x10 ohms No current 3 3 ALS-tannin-treated sample 32x10 ohms 28x10 ohms

It is noted that fibers treated in the presence of ALS tannin have a higher electrical conductivity than fibers treated without this tannin, and that fibers still have conductivity after dyeing, whereas reference fibers do not have measurable conductivity.

The treated fibers have a 0.3 μm thick copper salt coating. These fibers are used in the manufacture of fiber filaments, which are added in carding to 0.03% polyhexamethylene adipamide fibers with a thickness of 22 dtex (20 den) and a length of 150 mm. The obtained spun yarn is used as a single yarn in the warp of the fabric formed by the tuft of four yarns.

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Example U

A multi-strip polyhexamethylene adipamide yarn having a thickness of 17 dtex (15 den) and previously disoriented is treated with a 10% by weight aqueous solution of methadiphenol at 60 ° C for one hour, then rinsed with water at 1 * 0 ° C and dried at room temperature. This wire is then treated in the same manner as in Example 1, except that the copper-salt solution does not contain methadiphenol. The wire has a 0.1 / m thick copper salt coating after treatment. The mechanical properties of the yarn, in comparison with the properties of untreated similar yarn, are as follows: .Yarn 'dtex: Fracture' ' : 1 * 1,7: 32,65: 119,8: 'Untreated' 19,7: 63,9 g '32,6' 56,8 '95,8 [The yarn is then incorporated into the yarn made for the carpets by means of a compressed air nozzle, having a thickness of 2300 dtex (2080 den) / 136 filament that is teksturcitu British patent No. 1300379 described above, and measure the time it takes for half charge decay Rothschild elektrometrilä type, as described in UK patent No. 58l63.

Measurements shall also be made after this yarn has been dyed in a bath containing: - 0,19 g of yellow "Nylosane EL", sold under the trade name SANDOZ (yellow sour 17U), - 0,09 g of brown-yellow toner "Nylosane ERL", sold under the trade name SANDOZ (brown acid 2 ^ + 8), - 0.019 g of the blue dye "Nylosane EGL", sold under the trade name SANDOZ (blue acid 72), - 10 g of the anionic product "Lyogene P", sold under the trade name SANDOZ, - 30 g of the anionic product "Erional NWS ", sold under the trade name CIBA-GEIGY, - 1 em acetic acid to adjust the pH to 1+ - water to a total weight of 1000 g. The ratio of bath to material is 1 g of material / 3 50 cm bath.

A second dye is then carried out with a similar yarn and under the same conditions, but at a pH of 6 not obtained by replacing acetic acid with a buffer mixture of 2 g of crystalline monosodium phosphate with one molecule of water as crystalline water and 0,5 g of crystalline disodium phosphate with crystalline water 12 water molecules.

60571

The results obtained are shown in the following table, in which the values are compared with those obtained with a similar reference wire but not subjected to methadiphenol pretreatment.

Before dyeing After dyeing;

Reference sample Varies within 1 sec ... 25 min pH 3.9 15 min pH 5.9 15 min

Test sample Releases immediately pH 3.8 Releases pH 5.9 immediately It is seen that the antistatic properties of yarn pretreated with methadiphenol are good.

Example 5

A nonwoven layer is made of 99 x 9 weight # polyhexamethylene adipamide fibers with a thickness of 22 dtex (20 den), a length of 75 mm and dyed as described in Example 3, and 0.1 # similar undyed fibers. , but which have been treated as described in Example 1 to obtain antistatic properties.

2

The needled layer weighs 1 + 00 g / m and is needled onto the lower layer, which is a textile layer made of natural fibers. The underside of the layer is coated with acrylic resin used at 150 g / m 2 and containing 1+ by weight of a fatty acid condensation product sold under the trade name Hansawerke under the name "Durostat".

The needled combination thus prepared is used as a floor covering.

Its antistatic properties are tested under the following conditions.

The experiments are performed on samples after U8 hours in a room with a temperature of 22 ° C and a relative humidity of 1 + 0 #. (a) Determination of transverse resistance

The measurement is performed by means of a circuit to which a direct current generator is connected in series, which supplies two electrodes, between which a sample, the transverse resistance of which is to be determined, and an electrometer are placed. The current is allowed to flow for 60 seconds and the voltage is 500 volts. The electrometer indicates the amount of electricity from which the transverse resistance can be calculated. (H) Determination of charge sensitivity A sample resting on its back on a grounded metal plate is rubbed rapidly in the usual manner with a metal scraper grounded. The insulated electrode connected to the electrometer is pressed into the sample under a certain pressure. The amount of charge formed on the sample as a result of abrasion is read immediately from the electrometer connected to the electrode.

8 60 571 c) a half charge decay time in the current sample is allocated under the conditions described in the preceding paragraph b). The electrode connected to the electrometer is placed one centimeter from the top surface of the sample. Measure the length of time that elapses before the value of the charge read from the electrometer is halved compared to its initial value, which is determined while the electrode is placed.

(d) Passing test The sample is placed along its entire length on a metal plate laid on a substrate and earthed.

A subject with leather-based shoes walks along the mat four steps in the same manner for each sample. Upon reaching the end of the sample, the experimenter touches the electrode connected to the electrometer with his finger. The charge generated by the friction between the sample and the footwear is read from an electrometer connected to the electrode.

The same measurements are performed on samples similar to the mat described above, but containing 0.2% by weight of the fibers treated according to Example 1 to achieve antistatic properties.

The results obtained by measuring three times in each experiment are compared with the results obtained on a similar mat but not containing antistatic fibers are shown in Table 1 below.

9

Table I

60571 ‘Sample: Reservation time’ ‘Time that: Pass test ,: Transverse: | : stiffness, ^ l wear reserve: coulomb: resistance: ‘: Coulomb x10 | use pur-: -7: oIiniia:: / 2 * to fall:::: / cm:: _ half ar-::: ’: | voonsa sec--:::) __: _ | you _: _: _: | Reference: 900 '25: 5: 1,5. ΙΟ -? !? :! : 1600 and 23: T: 1.5. 10 ^: i: 2000; 21: 6.5: 1.5. 101 ^:: 99.9% treated- | 250: 3: 1.5: 5. 1011 | : »Fibers j J k’ i 1,5 · 5. 1011:: + 0.1% antistatic. :: other fibers * l80: 5! 1.3! 5 · 101 '| 99.8 Ϊ processing; TO j 2: 1,2: 2,5. 10 ':; ^ ttö »fibers; Il (0; = 0.7: io7: + 0.2% antistatic fibers [1T0 | 2: 1,1+: 1. 10:

It is noted that samples containing fibers treated in accordance with the invention have antistatic properties that are clearly superior to those of samples that do not contain these fibers, and that the higher the number of treated fibers, the better.

Example 6

The experiments described in Example 5 are performed on similar floor covering samples, however, at the application stage, the product "Durostat" contained in the acrylic resin has been replaced by the same amount of a similar product sold under the trade name "Tallopol" by Chemische Fabric Stockhausen.

The results are as shown in Example 5 in Table 2 below.

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Table II

‘Sample; Booking can: Time that | Passage test,; Transverse-:] 'lie, ^ [wear spare-' coulomb 'resistance:) [Coulomb xlO' ust pur- 'χ -7' ohms: / 2 'through' *:: / cm half ar- _ _:] ' flow second | | : ’] You‘ i:.

: Reference: 900: 25: 5 ’1.5. 10 ^ 3; ; 1600; 23; 7 = i, 5 · 1013::: 2000: 21: 6.5 | 1.5 · 1013 '*! 99> 9 # process- | 300 [T! 2, T: 2. 1012> 0.1% antistatic; 300; 8; 2 · 9: 3 · 10 ‘other fibers’ 350 ‘8’ 3: 5. 101: 99.8 # process-: 600: 5: 1.3: 3. 1012: Ace; ™; 6; ^ I * · ““:: ti of fibers: 1000: 5: 1,1+ ‘1. 103

As stated above, the antistatic properties of samples containing fibers treated in accordance with the invention are clearly superior to those of samples not containing these fibers, and that this improvement is greater the more treated fibers are added.

Example 7

A nonwoven layer is made of a mixture of 60% by weight of dyed polyhexamethylene adipamide fibers having a thickness of 22 dtex (20 den) and a length of 75 mm and 100% by weight of ethylene polyterephthalate fibers, also dyed, of a strength and length of the same, and to which are added 0.1% by weight, based on the weight of the fiber mixture, of polyhexamethylene adipamide fibers of the same strength and length, which have not been dyed but which have been treated as described in Example 1.

2

The perpendicularly needled layer weighs 500 g / m. On the wrong side, 150 g / m butadiene-styrene latex containing U by weight # "Durostat" is applied to the wrong side, followed by a second application of UOO g / m foam, which also contains U by weight # this product "Durostat". .

11 60571 This floor covering is subjected to the same tests as in Example 5 * Measurements are also performed on samples similar to those described above, but containing 0.2% of fibers treated to achieve antistatic properties. The results obtained are shown in Table 3 below.

Table III

‘Sample’ Charging force- ‘Time that: Passing test, * Transverse-:‘ ’lying, -12 '^ u ^ uu v & ra—: coulomb j resistance:

Coulomb x 10 'door pur-:, -7' ohms::: 0:. . . x 10::, 2 for beating::: / cm:::. half ar-:. : I: ‘flow in seconds:’:: ‘you:’:: Benchmark j 1000: 30 ‘5: 1.5. 10 ^ 3 ':: 750; 30: 3.5 and 1.5. 1013:; ; 700: 30; k, 5 · 1.5. 1013; : 6% polyamide: 6: 3! 3.5 · 10 ^: + · · 200: 5: 3: U, 5. 1011 and 0% polyester:. ::: fibers: 190 H: 3 [2. 1011:: + 0.1% treated fibers: 60% polyamide- 100: 5 \ 1: 3. 1C · 11 '. i + 0: 7: 0.8: 3. 1011: .40% polyester. :: ‘Fibers’ 1 + 5: 6 ’0.8: 3. 101 ''. + 0.2% treated fibers ': \:.' :!

As stated in the previous examples, the antistatic properties of samples containing fibers treated in accordance with the invention are clearly superior to those of samples not containing these treated fibers, and that this improvement increases as the amount of fiber added increases.

Example 8 The experiments described in this example are performed on carpet samples similar to those described in Example 7, except that in the application step, the product "Durostat" contained in the latex and foam has been replaced by the same amount of product "Tannopol".

As in Example 7, the results are shown in Table b below.

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Table IV

‘Specimen’ Charging force: Time that ‘Passing test’, ‘Transverse‘ thickness, ‘elapsed reserve] coulomb‘ resistance

Coulomb x10 'ust pur-', -7 'ohms • * ·. * x 1U * / 2 'to fall:: / cm:::: half an ar-' 'to its second' '' '' te '' 'jComparator j 1000 j 30' 5 '1,5 · ΙΟ "* - 3 :: 750: 30: 3,5: 1,5, 1013:; 700! 30: u, 5; 1.5 - io13;: 6θ% polyamide-: 130: 7: 1: 3. 10 ^: ester - i 200 i 8 2'5 2'5 * 10 ^ =: fibers: 120: 6: 1.5: 2.5 1012:: + 0.1% of treated-:::::: fibers:: ::: '60% polyamide- '250 j 7 .'1,5! 9 · 1011 FATHER' *,. 300: 6! 1.5: 9. 10U i .40% polyester. . . , ^ fibers; 350; 12 1.7 | 1. 10 2 i '+ 0,2% of treated fibers

The same observation as above can be made with regard to the improvement of the antistatic properties of the mat when fibers treated in accordance with the invention are added to the mat.

Samples of the products prepared according to the invention have been handed over to the "Institut National de Propriete Industrielle" on the basis of the invention. They comprise: - sample No. 1 polyamide 66 fibers treated as in Example 1 - sample No. 2 polyamide textured yarn containing yarn treated as described in Example 1.