DE2250352A1 - METHOD OF FLAME RESISTANT OF DRAFTED POLYAMIDE FIBERS - Google Patents

Description

Yerf Ahren to Flammenbestä & digaaahen of verstreökten polyamide threads

The invention "relates to flame-resistant polyamide fibers and a method of making the same.

It is known polyamides; for the purpose of improving their resistance to burning to behänd0In ₀ So, e.g. Polyamide sleeves contain flammability reducing agents before molding? See USA * -Patentsöhrift 3 418 26? · It is also known to apply fire-resistant coatings to textile materials that contain polyamide threads. However, these previously known methods are not fully satisfactory because they lead to the development of a harmful chemical activity or can change the properties of the sextile fabrics.

The invention provides flame-resistant, drawn aliphatic marriage Polyamide threads are available, which are characterized in that they are about 2 to 18, preferably 6 to 10 percent by weight (based on the weight of the threads)

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RD-1882

1.4 »5.6» 7 f Y-hexachlorobicyclo- / ?. 2. 17-5-hepten-2,3-dicarboxylic acid (Hexachloro-endo-methylenetetrahydraphthalic acid, "Chlorendic Acid "), hexachloro-endo-methylene tetrahydrophthalic anhydride, Tetrabromophthalic acid, tetrabromophthalic anhydride, tetrachlorophthalic acid and / or contain tetrachlorophthalic anhydride. The invention also relates to a method for producing flame-resistant threads from such threads Polyamides, which is characterized by »that one the Threads treated with aqueous fluids containing one or more these contain halogen compounds. The treatment with the aqueous liquid is preferably carried out at temperatures of at least 97 C at pH values below about 5.

The threads prepared according to the invention contain 2 to about 18 percent by weight of one or more of the abovementioned halogen compounds. The connection in question is presumably contained in the threads in the form of a salt with the terminal amino groups of the polyamide molecules and / or as a coordinated molecule; because it can be extracted practically completely from the threads. For example, _# hexachloro-endo-methylenetetraliydr © phthalic acid with aqueous. Extract solutions containing a base such as ammonia, sodium carbonate or sodium hydroxide in concentrations of 1 to 5 percent by weight.

The threads produced according to the invention show a considerable reduction in their burning capacity compared to untreated threads. In the vertical flame test, an excellent rating is obtained if the content of the halogen compound is at least 3 percent by weight evaluated as selbstvcrlöschend or nearly self-extinguishing upon removal of the .Flaiaiae, and threads to IO percent by weight contained in the halogen compound 6, provide a preferred Aufi- · guide die illustrates the invention "Although one can Avah enlarge the amounts than 10 percent by weight of these halogen λ :: ^ 1) indications

309816/1107 owginally inspected

RD-1882

inlays in the threads ^ ax ¥ resistance of the threads against burning we are therefore not proportional elevated.

Since the halogen compounds used according to the invention with If the polyamides react, it can "at elevated temperatures a chipping discoloration of the treated threads can occur. At moderate temperatures, however, i.e. in the temperature range from about 130 to 150 ° G, or with only brief exposure suffer from higher temperatures in the order of 200 C. the threads according to the invention hardly, if at all, a color change. This is a significant advantage in comparison for the treatment of polyamide melts with the halogen compounds. Since the halogen compounds are also used to treat threads that have already been stretched, Disadvantages arising from the stretching of contaminated Polyamide threads could result, avoided.

The method according to the invention produces flame-resistant threads by treating drawn polyamide threads with aqueous liquids which contain one or more of the halogen compounds mentioned. The aqueous agents containing the halogen compound can be padded onto the threads and the treated threads can then be heated to an elevated temperature, for example by passing them over heated rollers, through hot air ovens and the like. Suitable temperatures are in the range from 97 to about 140 ° G. Elevated temperatures are used to increase the rate of absorption of the halogenated solution by the filaments and to facilitate evaporation of the water. The treatment liquid can optionally also contain a dye.

According to a preferred embodiment, the polyamide threads treated in an aqueous bath, the Hexaehlör-endomethylenetetrahydrophthalssHjee contains and on an elevated

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Temperature, for example at least about 97 C and preferably at 98 "to 100 ° C. At temperatures below 97 ° C, the hexachloro-endo-methylene-tetrahydrophthalic acid such a low water solubility that the fabric does not is evenly penetrated by the connection. The pH of the aqueous bath is preferably not higher than 5% and for best results it should be between 2 and.

The aqueous bath can be mixed with organic acids or with mineral acids, such as acetic acid, formic acid, oxalic acid or phosphoric acid, are acidified. In the first part of the treatment you can the pH value may be relatively high; however, it should be reduced to 2 to 4 before the end of treatment. Low pH values make it easier to take off the bath. And a strong uptake of the halogen compound by the wires.

According to a particularly preferred embodiment of the invention, polyamide threads are treated with ilexachloro-endomethylene tetrahydrophthalic acid in the course of their production. In this sense, the acid can be continuously introduced into threads, yarns, cables and the like after drawing and before opening to form the package if it forms a component of lubricating finishes, re-strengthening baths or other treatment agents. If the filaments into short fibers, z _o p staple fibers to be processed, they can be treated by the Dchnoidvorgang.

However, the threads can also be treated as yarn after they have been opened. For this purpose, one can use known pack dyeing processes, whereby the high temperatures and low pH values required for the process must of course be maintained during the treatment. The threads can also be tied up after they have been processed into a textile fabric by irrkm rind. The halogen connection can be used in conventional baths, ·, ■ :.) υ; ·] <: for processing textile material cd

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can be used, e.g. to dye liquors, or it can be used in a special bath with which the fabric is additionally treated. Treatment of the threads can before, well, during dyeing or instead of dyeing take place. The threads can be treated in the form of clay nonwovens, Knitwear or knitwear or woven fabrics. Also carpets, upholstery, artificial hair, Wig fibers and the like can be made more flame resistant in accordance with the invention.

. The amount of halogen compound in the bath can vary in the range of about 1 to 10 percent by weight. If nan the anhydrides When used in aqueous baths, there is considerable hydrolysis to the acid in question, and the filaments can then take up both free acid and anhydride '.

Except for the halogen compound, the acidifying agent and optionally a dye, the aqueous treatment baths can contain small amounts of organic liquids, wetting agents, Contains buffers, whiteners and / or complexing agents.

The polyamides which can be used according to the invention are fiber-forming, long-chain, synthetic polyamides with recurring amide groups of the formula

O
-C-NII-

as an integral part of the polymer chain. Particularly polyhexamethylene adipamide (nylon 66) is preferred. Other suitable polyamides are, for example, polycaproic acid amide (Nylon 6) and the polyamide from bis (4-aminocyclohexyl) methane and dodecanedioic acid. Also copolyamides, such as those made from hexamethylene adipic acid amide and caprolactam, can be used.

In the following examples, all percentages relate

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ORIGINAL INSPECTED

on the weight, in the case of polyamides on the weight of the thread and in the case of liquids on the weight of the solutions. The vertical flame test described in ASTM test standard D626 is used to determine the flame resistance of the threads produced in the examples. The relative viscosity (RV) is the ratio of the absolute viscosity of the solution to that of the solvent at 25 C. The solvent used is a mixture of 90 percent by weight formic acid and 10 percent by weight water, and the solutions have a polyamide content of 8.4 percent by weight. The hexachloro-endo-methylenetetrahydrophthalic acid content of the threads is determined by coulometric chloride analysis according to the method described by Cotlov and co-workers in "Journal oi Laboratory and Clinical Medicine", Volume 51, 1958, pages 461-468, and those found Values are converted to hexachloro-endomethylenetetrahydrophthalic acid. In practice it has been found that the weight gain of the threads on treatment with the halogen compound does not deviate by more than 2 $ from the content of the halogen compound determined by analysis. Therefore, the increase in weight can be used as a measure of the content of the halogen compound. The importance of this approximation is confirmed by the flame behavior, in which threads are flame-resistant after a weight increase3 of at least 6% , ie often extinguish themselves within a few seconds, for example less than 30 seconds.

example 1

Polyhexamethylenadipinyäureamid, which, based on weight the polyamide, $ 3.5 of an ethylene oxide condensation product and 0.5 / ^ 4,4'-But3''liden-bi3- (6-tert.butyl-m ~ kreaol) contains, becomes a 320-ply yarn with a relative viscosity spun by 56. The yarn is stretched 3.0 times to a denier of 18.5 denier.

The yarn is processed into a knitted fabric and this is dyed using the following process:

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An aqueous flot of paint is made using 2 kg Water, 25 ml of a 1 percent solution of tetrasodium ethylenediamine tetraacetate, 16 ml of a 10 percent solution of the disodium salt of disulfonated monoalkyldiphenyl ether, 50 ml of a 10 percent trisodium phosphate solution and 100 nil a 10 percent mononatriuin phosphate solution; 100 g each of the knitted fabric. The pH of the dye liquor is set as indicated in the table below. To this bathroom one sets first 50 ml of an O, 4rP ^ o ^ entigen solution of CI. Acid Blue 25 (C.I. 62055) and then the knitted fabric to be dyed. The dye liquor is then used in the course of 45 to 60 minutes brought to boiling temperature and 30 minutes to boiling temperature held. A boiling solution of 12 g is then added Hexachloro-endo-methyietetrahydrophthalic acid in 200 ml v / water to, adjusts the pH value, heats the dye liquor to the boil for another 30 minutes and measures the pH value, the dyed knitted fabric is rinsed in cold water for 10 minutes and air-dried. The content of hexachloro-endo-methylene-tetrahydrophthalic acid in the threads is determined and the flame resistance of the threads is measured. The results are shown below Tabel.

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C3

Try IJr.

- -i _,; η ■ -

2.5

IiU. j. UiJ.53 -UlJ-Tj uSr

after treatment with the

The sin of the paint process

Weight gain, ^ chlorine compound, fo * "vertical flana test

Release side, sec

Burn

2 time, sec

Length, cm

Hexachior-endo-methylenetetrahydrophthalic acid,

2.5 3.2 3.9 5.0 6.3 6.9 2.1 3.4 4.0 4.9 5.9 6.8 10.5 10.6 8.4 4.8 1.7 0.9 9.0 9.6 6.8 3.8 0.8 0.2

4th 3 4th 6th 11 140 0.6 0 0 0.6 0.6 21.6

Example 2

Poly (methylene-di-1,4-cyclohexylene-dodecanediamide) from dodecanedioic acid and bis (4-aminoeyclonexyl) -raethane with a trans, trans stereoisomer content of $ 70, is derived from the Melt spun into a 36-ply yarn and down to a total titre stretched out of 60 den. The 60 denier yarn becomes too blown in an 8-string atlas and colored as follows:

A dye liquor of 100 ml is prepared by adding 0.025 g of a condensation product of 20 mol of ethylene oxide and 1 mol of a monohydric aliphatic alcohol with 18 carbon atoms, 0.050 g of Acid Red 151 (CI. 26900}. And formic acid to to a pH value of 3. Each addition of a 25 g sample of the fabric, the dye liquor is heated in the course of 20 minutes to 71 ° C. and then 0.38 g of a mixture of «.- and β-methylene is added After 10 minutes, the pH is brought back to 3 by adding formic acid and the dye liquor is heated to the boil Taking a portion of the dye liquor, dissolved in this part of the Hecaehlor-endo-methylentetrahydrophthalsäure the solution was then added back to the remainder of Farbflotfce to and. the dye liquor is kept for 2 hours at boiling temperature and the tissue then at 60 ° Q in water rinsed until the rinse water is clear. The treated fabric is washed for 30 minutes in 100 ml of a bath which contains 0.025 g of the above-mentioned ethylene oxide condensation product and 0.013 g of acetic acid. The fabric washed in this way is rinsed with cold water and dried in a hot-air oven in a tension-free state at 82 ° C. The fabric is then heat-set for 60 seconds at 190 ° C. in a tension-free state. The threads contained 6.2 ⁰ J * Hexaehlorendo-rnethylente brahydrophthalsäure and extinguished after a 3 f3ekunden permanent ignition in about 1.3 seconds, the burning-off of about 6.3 cm by itself (these values are mean values of 5 determinations on aii £ four samples).

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Example 3

A sample of the textile fabric described in Example 1 "is treated at 27 ° C with a pad bath containing 200 g of purified natural resin ether, 10 g of acetic acid, 30 g of a mixture of sulfated, long-chain aliphatic alcohols and 10 g of a condensation product of 9 moles of ethylene oxide per liter and 1 mole of nonylphenol. The knitted fabric is padded by passing it between two rollers, the lower one of which revolves in the padding bath. The padded knitted fabric is heated to 100 ° C. for 10 minutes with steam, then rinsed in cold water and dried dried knitted fabric is padded with a paste containing 7 parts of hexachloro-endo-methylenetetrahydrophthalic anhydride, 5 parts of thiodiglycol, 2 parts of fatty acid amide, 2 parts of a non-ionic surfactant, 55 parts of purified natural resin ether, 5 parts of benzyl alcohol, 0.5 parts of the sodium salt of a sulfonated alkylbenzenes and 0.5 part of 2-ethylhexanol Steamed i 100 ° C, washed for 3 minutes at 60 C in a solution containing 2 g of a condensation product from 1 mol of a mono-solid alkanol with 13 carbon atoms in the molecule and 20 mol of ethylene oxide per liter and 5 g of Lauryl trim e thy lammoniurn br omid per liter, and then dried at 80 ° C. The dried knitted fabric shows a weight increase of 17.7 ° and extinguishes by itself after ignition for 3 seconds in 14 seconds after 1.3 cm has burned off.

For β ρ ie 1 4

The procedure is as in Example 3, but using tetrabromophthalic anhydride. This is where the textile experiences an approximate total weight of 18 ^. After 3 seconds longer Ignition, the fabric will self-extinguish in 13 seconds after 3.2 cm has burned off.

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Example 5

The knitted fabric described in Example 1 is treated as follows, using a ratio of dye liquor to textile fabric of 50: 1: The knitted fabric is added to water at room temperature, whereupon for every 10Qg; Textile added 0.25 g of tetrasodium ethylenediamine tetraacetate, 1.5 g of the Hatriusj salt of a sulfonated aromatic hydrocarbon, 0.5 g of trisodium phosphate, 0.5 g of Acid Blue 78 (GI 62105) and 2 g of MononatriuiBphösphat. The pH of the dye liquor is 6.0 and is reduced to 5.5 with acetic acid. The dye liquor is heated to 99 ° G within 45 minutes and then treated with a 160 ° C solution of 12 g of tetrabromophthalic anhydride in 25 g of benzyl alcohol. The dye liquor is held for 60 minutes at boiling temperature and then has a pH value of 4 "The treated" fabric is rinsed for 10 minutes at 21 ° C _t after which the excess water is removed and the fabric is heated 10 minutes at 150 C. The weight gain of the Fabric is $ 8.7, and after 12 seconds of sinning, the knitted fabric burns for just 14 seconds over a length of 3.8 era,

Example 6

A bath is made of 3500 ml of water, 25 ml of an i percent solution of sodium ethylenediamine tetraacetate, 16 ml of a 10 percent solution of the disodium salt of disulfurized in monoalkyldiphenyl ether, 50 ml of 10 percent trisodium phosphate solution and 100 ml of 10 percent sodium sulfate. The pH of this bath is adjusted to 2.5 with 10 percent phosphoric acid. Then 50 ml of a 1 percent solution of Acid Blue 78 (CI. 62105) and 100 g of the knitted fabric described in Example 1 are added .? g Tetrachlorphthalsäureainliyclrid placed in 500 ml of water and because "Gemiöch further 30 minutes kept at boiling temperature Kunmeln - is de c pH 2.5 The Gevd.rk 10 minutes in kali-em V'aaser flushed what.

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the excess water is removed and the fabric on
the air dries. ]) The increase in weight is 2.75 ° ß> and the content of flannel retardant, calculated as tetrachlorophthalic acid, is 2.9 5 ^. After ignition for 3 seconds, the fabric burns for 3 seconds over a length of 0.6 cm.

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Claims (1)

EoI. du Pont de Nemours and Company, V. ED-1882- -, Claim Method for making polyamide threads flame resistant, thereby marked that the threads with an aqueous Preparation of 1, ^, iJiGjTjT-Hexachlorbicyclo - ^^ iy '^ - hepten - ^^ - dicarboxylic acid, ν tetrabromophthalic acid and / or tetrachlorophthalic acid and / or anhydrides of these salsa treated and then dried. - .13 3098 16/1107 BATH ORIGINAL