LT3089B - Strech-spinned artificial filaments based on polycaprolactam and manufacture thereof - Google Patents

Description

In the case of general spunbonds, the threads leaving the filament during spinning are removed at speeds greater than 3000 m / min, whereas in the case of typical forming, the maximum spinning speeds are about 1200 m / min.

In general, fast spinning is superior to traditional spinning because of its higher performance. In some cases (particularly in the case of polycaprolactam) it is possible to save on one technological operation, the stretching of the thread, depending on the circumstances. Another advantage of high-speed spinning is that the yarn spinning and winding processes are, as a rule, less dependent on the moisture content and ambient room temperature than traditional spinning, ·, · ', ¹ ..:. ·,. ··· . '·'. / way. Further, compared to conventionally spun yarns, yarns that have been spun fast and wrapped ¹ in packaging still show better performance during storage until further processing. High-speed spinning yarn Particularly suitable for stretch-texturing, stretch-throwing and stretch-spinning.

The stretching-texturing operation is understood to mean the simultaneous stretching and texturing of the filaments, whereby texturing results in a specific fiber structure due to the directional orientation of the macromolecules. This results in higher elasticity, foam (volume filling) and thermal insulation compared to smooth yarns. Such yarns may be greased and / or twisted to improve further processing. '.;' ./'/

For making warp knitwear or fabrics / in a knitting machine. or in looms a large amount of yarns need to be / arranged as a warp parallel to each other. For this purpose, hundreds and thousands of threads are wound together in one so-called

A,; ///. ^? · 3 y <

throwing shaft. In addition, in order to improve the yarn's compactness and stability, the yarns 7 / yarns / 7 are stapled together in a r i eb in ami, / p a r a f inu oj ami or / this icht Uo j ami,

Further increasing the number of threads may require the connection of 5 of a number of such spindles. The production of the thrust shaft can be combined with the total stretch of the ball (stretch-throwing), yes. The same is true with 'yarn ball sanding', whereby the yarn applied to them is better protected mechanically by the coating of the sanding agent.

The stretching operation is known to be connected

.. to or integrated with the spinning operation.

EP-B 201, 189 discloses the production of polyamidofilaments by spinning from a melt other than

- that the melt of the polymer blend having a low molecular weight additive, water, with a relative viscosity of 2.0 to 3.0 (measured in 96% sulfuric acid) is extruded to form filaments. cooled, cooled filaments stretched at speeds greater than 3200 m / min. No polycaprolactam filaments produced in the presence of · dicarboxylic acids as chain regulators are described here.

DE-A 4, 019, 780 describes a process for the production of polycaprolactam in the presence of dicarboxylic acids acting as chain regulators. From there polycaprolactam (relative viscosity

RV = 2.36) by rapid spinning at forming speed

Threads produced at 4250 m / min have standard thread strength and • elongation at break.

The disadvantage of stretch spun yarns obtained by rapid spinning, or stretched35, is that they have a tensile strength index / lower / that of conventional / spun yarns and that they are stretched to the same degree of rupture;

R is also a textured-yarn indicator. / Another disadvantage of such fast spinning yarns is the change in tensile strength during tensioning, which is measured by measuring the tensile force as a function of the length of the yarn (tensile ·· force-elongation curve). These changes are not large enough, i.e. this curve is usually 'flat'.

Compared to high speed spinning polyamide. * ·· '·? 'R, R.

(Polyhexamethylenadipamide), a fast-spinning polycaprolactam yarn, with the same yarn spacing, has another disadvantage after stretching-texturing, which is worse retention of foam.

. The object of the present invention was to make high-speed spinning yarns of polycaprolactam which would not have the disadvantages mentioned above. Such 3ίΰ1άΐ .: - ρϊίνι1ό ^ - ρ33.ΐ2γιύέ {: ι improved tensile force / deformation, ie, / steeper tensile-elongation curve. -cracking _; force ^; and, in the case of textured stitches, an improved /

--e, pUblumo: slideshow.7 / - '/ -?'? / i '/' // - / -. ^;

-According to '/. / to? - / t / a .//? rr '/ was a R created jp ^ bnks with spellbinding threads.

R R / R ?, // 'R /// ?, / /.' to AR / - · / bb b 'Rb- - /.' b R Z R '// b 7'A' Ab / R

The method of making these yarns was also developed and their application in textile manufacturing was found.

According to the present invention there is provided a spun melt containing the above polycaproactam, and the resulting and cooled filaments are formed at least / [3600 + 1250]. (3, 0 - RVJ] m / min; optimal minimum speed is [3800 + 1250. (3.0 - RV)] m / minR At higher than [3600 + 1250. (3.0 - RV)] R m / min - An unexpected increase in breaking force occurs for velocities, which is explained by the choice of spinning speed / above [3600 + 1250. (3.0 - RV)} m / min at /.> j '. LT 3089 B, the greater is the degree of increase in the breaking force of the spun yarns, thus our experience shows that 'commercial polycaprolactam either does not show this effect at all or shows only a slight degree (see comparative example). that at spinning speeds below [3600 + 1250. (3.0 - RV)] .m / min, this · effect does not occur 3

The maximum spinning speed limit is n © greater than 8000 m / min and is mainly dependent on the viscosity of the spinning melt and the spinning machine used.

33 // 77-7? 3 - //: F _t , ', ·? · / ·· ®? 337 3 _O 7 /.- 33-: // 3373 // 7 3/33 33'3'3'7' 337 \ ¹ 3 ^; 3 //: 373333 '33333' 3/73 /: 3? · 3 "7'333. · · 7

The relative viscosity RV of spun polycaprolactam is generally in the range 2.0 to 3.0 (measured by dissolving 1 g of polycaprolactam used in 100 mL '96% sulfuric acid at -25 ° C);

BilSIB '^^ W ^ s ^' i3? ^ K ^ a <;3RV'7^; yr </ otéryiçe / 7pai © /: / 2to: 3 ^; 72 to ^ 73 polycaprolactam RV prevents stable spinning of the fiber. ^'1 according to the invention the cellulose yarn relative viscosity RV is between 2.0 and' 3.0 (measured hardness solution 'with' 1 ¹ g 100 ml polikaprolaktamo € 9% - sulfuric acid ines' 25 DEG C. ©); · The most appropriate 'RV is'

333; 333ί $ £, ^^ 1: ©; | β '^

According to '; the invention is' used in polycaprolactams produced by the presence of at least one dicarbonyl:

; 3: 3/3: 3 :: brains; 3; 3 ///; brains3 / 37 / grandfather: / 33 / liked7;

function. Such polycaprolactags are known, e.g., from

3 | 3373Wš3O ^; feBB; S3 ^^ ^:; -77777'77 / 7 ^; way7'777: '; / f / 7 ": 3; 7 ^/ / f3 // 3 / ^F:. · - · - · / '' / - to - / F'- · - // - f. . /.77;y/7/. .. 6 -,. · /;

; For the polymerization of polycaprolactam, it is expedient to use water and dicarboxylic acids as chain initiators at process temperatures of 23 ° C to 300 ° C, preferably

- 240 ° C to 290 ° C:

Polymerization adapting devices are known in the art and described, eg., Patents DEASen 2, 448, 100, 1, _495, 198 and EP-B 20, 946.

The amount of water used as initiator in the reaction is' 7, 7 7, / 77: 77'7 '''' / 7. ^{; /7.7α7,:} /// · / /·./.·* 777: ..:, a / /,7//7/'./7 7 / 7.7 / 7.7 / // 77/7/7 , /, 7 .. _; / 7 //. · _: ·. , / 7 // 7. '7 ·· /' / 'predominates between 0.1 and 5 weight. most preferably between 0.5 and 3.0% by weight (based on the weight of polycaprolactam).

The dicarboxylic acids used are those which act as bifunctional <7 chain regulators during the hydrolytic polymerization of caprolactam and do not decompose, discolour or undergo any polymerization or spinning. Dicarbonic acids which, for example, may act as chain terminators due to the formation of cycles, are not suitable. Examples of unsuitable dicarboxylic acids include the succinic and phthalic acids which act as chain terminators by cyclization.

'·,' 7,. / '·'. 7a. ·· '/ »' · '/' · / · / 7 /. , ·· '; . · '·· · ^\:. ·' Ί · · · α / '' 7/7 ^7; ' ^: ·'/;'·. ·.

Suitable dicarboxylic acids are, for example,

C ₄ -C ₁₀ -alkandicarboxylic acids, such as: adipine, pimelin,. cork, azelaic, sebacic, undecanodic and dodecanodicarbonic acids;

- adipic acid is most suitable, -. . / '7 ('

C ₅ -C ₈ -cycloalkanedicarboxylic acids such as: cyclopentane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarbonic acid; most preferably cyclohexane-1,4-dicarboxylic acid,. .

benzene and naphthalene dicarboxylic acids with up to two sulpho groups, including their corresponding alkali metal salts, whose carboxyl groups are not adjacent, such as terephthalic, isophthalic, naphthalene-2,6-dicarboxylic acid,. 5-sulfoisophthalic acid;

the most preferred are -terephthalic, isophthalic and 5sulfoisophthalic acids and mixtures thereof, '

N 1 -C 8 -alkyl-N, N-di (C ₄ -C ₁₀ -alkanecarboxylic acid) amines as N-methyl-N, N-di (caproic acid) amine, N-methyl-N, N-di (acetic acid) ) amine,

1.4-piperazine-di (C 1 -C 8 -alkanecarboxylic acids) as

1,4-piperazine-diacetic acid, 1,4-piperazine-dipropionic acid, 1,4-piperazine-dibutanoic acid, 1,4-piperazine-dipentanoic acid, 1,4-piperazine-dihexanoic acid. acid, preferably 1,4,4-pierazin-diacetic acid and 1,4-piperazine-dipropionic acid.

Polyamide yarns with dicarboxylic acids containing tertiary amine groups can be easily dyed with anionic dyes ... This is desirable in cases where high intensity colors are desired. As a rule, sulphide-containing fibers are easily dyed with cationic dyes. Conversely, such fibers are susceptible to anionic dyes found in, for example, foods! and in beverages, diminished, which, as it reduces the fiber (distance. .3;

3.5

Dicarboxylic acids are appropriate ^ / · / at the beginning of the polymerization zone to be? their complete mixing with. polymerized with duck melt. Dicarboxylic acids can also be added before or during polymerization. .

The amount of dicarboxylic acids added as a rule ranges from _x

0.05 to 0.6, in particular 0.1 to 0.5 mol%, based on caprolactam.

'7'7 · .4-' ·· // '4 <· 7 _: <. · V:' · / 7/4 // 'y..yy / 444 ./.-/ -y .4 9''-.' 77 4- /. · / · '/. 7 ';'. '. · /

Besides already. The dicarboxylic acids mentioned can also be used as chain regulators in the presence of N, N-di - ((- C / 15 alkyl) amino- (C ₂ -C ₁₂ alkyl) amines to improve the dyeing of the yarns by anionic dyes.

'y ^: y. - · / · // · '·· - / · _ / .. 4- / 4 //. : / '' / - // //: / ·,; // - 777 / y: .. 4./-/4-/- / / - / - 4- / ^- - / - 7 // - / 4 .// 4 ..//'''-'- v / '// .. · - /4-1-/77/.'-·//.·'

74 / · /.;. // ·,;. / 4 - /'/·.-. 44. '4 .. · // ... ·; /, .. ···. ·. 4 ς · 4 //// 74 // 4 7, // ... y 'yy' y, 4/47 / - '·, /. . 4 ^.; 7 · ,, '/ -'; · '// ·.; / · * - · '. , - ^: 7-. · '/./'. 4 ·· // - 7 // 74

Examples include 2-diethylamino-1-ethylamine,

6-dimethylamino-1-hexylamine, 3-dimethylamino-1-propylamine, 3-diethylamino-1-propylamine, most preferred is 3d-dimethylamino-1-propylamine, 3-diethylamino-1-propylamine.

N, N-di - {(- (C ₁ -C ₄ alkyl) amino- {C ₂ -C ₁₂ 25 -alkyl) amino diamines are preferred. Their content usually ranges from 0.05 to 0.3%, preferably from 0.1 to 0.3 mol%, based on caprolactam. A content of less than 0.05 mole% does not provide a slight improvement in coloring properties; at greater than 0 .3 mol%.

the efficiency of these diamines as chain terminators increases too much.

In addition to the dicarboxylic acids mentioned above as chain regulators: primary monoamines can also be used to reduce the amount of caffeine groups in the product and to improve its melt stability.

³ '

Suitable primary monoamines are C ₄ -C ₁₂ -alkylamines and / or (3) as: bu t ii-, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 7 carbonyl; dodecylamine, phenylmethyl, ifenylethyl, phenylpropyl and phenylbutylamine; hexylamine, octylamine, decylamine and phenylethylamine are preferred.

The amount of added monoamine primary monoamine usually ranges from 0.05 to 0.5 mol%, most preferably from 0.1 to 0-4 mol% based on caprolactam.

In general, the polymerization can be carried out at pressures of 100 to 2000 kPa. Preferably, continuous polymerization is carried out at a uniform pressure in the range of 100 to 190, preferably 100 to 170 kPa (measured in the vapor phase above the polymerization zone, when the alloy is maintained at 0/1 to 0.5, preferably 0.1 to 0.4). weight% water content). This means that the excess water introduced into the reaction zone at the top, depending on the pressure present, is constantly distilled to maintain the above mentioned amount of water.

25 'The polymerization process generally lasts from 5 to 20 h' (most preferably 8-12h) and depends on the desired properties of the product.

Polycaprolactam is preferably removed from the polymerization zone at the bottom7 / 7

The amount of Z77-sulfated dicarboxylic acids (to be hydrolyzed on the polycarboxylate and then / analyzed) in the extracted and dried final product generally ranges from 5 to 60 / mMol / kg, most preferably from 10 to 50 mM / kg. Below 5 mMol / kg not available

y, 7 · ... 10.

a desirable improvement in the properties of the spunbonded yarn. At / above 60 mMol / kg, the relative viscosity required to obtain the polymers and thus the desired molecular weight cannot be achieved.

'· ///? 't // ·.: + 7.-. t / 7 ·· '' -y / - / Λ,: 7 '·' · '' / 7. .7 -.y? ./ -.

If the final product also contains chemically bound diamines, the amount should be in the range of 5 to 30 mMol / kg (most preferably 10 to 30 mMol / kg), with the amount of chemically bound dicarboxylic acids. as a rule, in the range of 10 to 50, preferably 15 to 50 mMol / kg.

The amount of monomeric and oligomeric residues to be extracted in the '' andene 'is selected from 0 to 2, preferably 0 to 1% by weight of polycaprolactam in spun-ready polycaprolactam. The amount of water in the spinning polycaprolactam is usually below 0.4, preferably 0.02 to 0.15% by weight.

The untwisted yarns according to the present invention have an elongation at break of 30 to 100%, preferably 40 to 90%. Thanks to the thread twisting operation, the elongation at break can be further reduced.

Polycaprolactam prepared for spinning, as well as the yarns obtained from it, may have the usual additives and processing aids. These substances are generally present in an amount of 5, preferably up to 3% by weight, based on the total weight of polycaprolactam

Common additives, for example, are antioxidants, anti-stabilizers and thermal-degradation and ultraviolet rays, paints, pigments, mattresses and antistatic agents. 7 '11. Antioxidants and thermostabilizers. -is, eg _: sterically blocked phenols, hydroquinones, phosphites and their derivatives, and substitutes for these groups, mixtures of these compounds, as well as copper compounds such as copper 5 (I) iodide and copper (II) acetate.

Examples of UV stabilizers include resorcinol, salicylate, benzotriazole and benzophenol, which may be added in amounts up to 1% by weight; divalent manganese compounds are also suitable for this.

Suitable dyes include organic pigments and common dyes for spinning fluids such as chromium or copper co-complexed compounds, as well as inorganic pigments such as titanium dioxide and cadmium sulfide, iron oxide or soot.

Common materials such as polyalkylene oxides and their derivatives may be used as antistatic agents.

Additives may be added at any stage of the production of the yarns of the invention, but it is expedient to add a stabilizer in advance so that their protective action is apparent from the outset. On this basis, stabilizers are added already during polymerization, provided that they do not interfere with this process.

According to the invention, the yarns produced are known to be stretched, twisted, stitched, stretched (rolled), stretched-stranded or stretched-textured.

Stretching of so-called plain yarns can be assimilated to fast spinning or can be done separately.

Stretching-throwing stretching-texturing and stretching-grinding operations are usually performed separately from fast spinning operations.

3089 8

The yarns produced according to the invention can, as a matter of course, be processed into fibers. Textiles can be made from weaving or knitting.

The instant spun yarns of the present invention are superior to existing ones in that they have improved tear strength. are characterized by a steeper tensile force extension curve and. has a more stable foam.

Based on observations to date, these yarns have a smaller amount of -'- strain defects than the prior art fast-spinning polycaprolactar yarns.

The following studies have shown that the polycaprolactam used according to the invention is reduced

8 //// ·:; //.: //-/./7-///7 :: /.//7 7 /// -, //: / - / 7: / -. 87 / 8 / -: /: 7 /: - /: ///./,/7/: / 8: -7888.7:; / 77. ' 8- · //:./7/8777/--: 7/8: / 7-, 8888: ///: /.7-./ • the elasticity of the melt, as well as the special process of forming the filaments from it morphology of polymeric crystals. It is believed that the improved properties of the yarns of the invention are related to the special elastic properties of the polymer melt and the specific fiber morphology.

EXAMPLES

/. - ..7 7 .-, / ... - · ._. ·. ·, 7.- -. / -88 / 8 · $ ..: -..- 8- / / - /// - / y. / · .. ._. 8-8:. ·· :: - 'a \ /.-/. · -. · /8./: // -... '_; / ·. -7.88 '/'.// 87 /.7/,: /, / 8-8 ...

The VK-type tubular reactor described in EP-A 20, 946 with stirring of the contents of the first reaction zone was used for the synthesis of polycaprolactam; The reactor has a volume of 340 1 and is heated by oil.

The relative viscosity RV of polycaprolactam and the spun yarns thereof was determined by dissolving 'Ig polymer in 100 ml 96% w / w sulfuric acid at 25 ° C.

The moisture content of the material was determined by a vapor pressure measurement method using an Akerman instrument.

'Y · ^; / 13 • The content of chemically bound dicarboxylic acid and 7 chemically bound dramin is derived from the amount of additives. Their amounts can also be hydrolyzed by polarization of polycaprolactam in dilute mineral acid followed by analysis of the resulting hydrolyzate.

Polikaprolaktamo melt elasticity is characterized according to the invention with dicarboxylic acid produced by the elastic flexibility of samples _e S ratio of propionic acid with the standard product flexibility J _eikūntr an identical sample viscosity. J _e and J _ekont * _{r are} determined by measuring the oscillatory displacement.

ΐ7ΐ5 '/; 7Υ · / Υ2ν ///:? 77Υ? ΐ / 7) 7) /?' Υ) /

Measurements were made on a dynamic rheometer-spectrometer RDS2 (Rheometrics) at 250 ° C with a displacement amplitude of 0.3 and a plate-to-plate measuring system (diameter 25 mm, distance 1 mm). Was

- the integral modulus G 'and the loss modulus were measured

G ”at an angular frequency of 0.3 to 100 rad / sec. The measurement curve recorded the angular frequency to which the loss modulus reached G = 10 ³ Pa. ElasticityJ _{e is} calculated from that point. of the integral module G '(equation 1):

Je = G '/ (G') ² = G '/ 10 ⁶ Pa ² ' (Equation 1),

Similarly, the flexibility of the same viscosity sample with propionic acid was determined. The .30 elastic · ratio R of the melt was calculated as the ratio of the following values (Equation 2):

'(Equation 2),

R expresses a rheological size that allows for very precise identification of differences in the elasticity of the melts.

/ The elongation was determined using a UsterTensorapid-I instrument with a POY sample length of 200 mm and a stretched and textured yarn of 500 mm. The test time before the thread breakage was 20 ± 2 seconds.

In the case of POY specimens, the pre-tensioning force was 0.025 cN / dtex, in the case of stretched yarns 0.05 cN / dtex and in the case of textured yarns 0.2 cN / dtex.

Calculated by estimating the thread linear density. breaking force 10 (specific breaking force} is found from Equation 3:

. "—- f '' ·· ·.

R _H = F _H / Tt _v (Equation 3), '/, - /7.-/-/''5' - '. C./..555/.7/5/7---7·; 7 '''· //,.---..-/:/7- /' / ... 7.5.// .-- + --- / - / 5.- '· /' /, where F _h is the rupture force (cN) and Tt _v is the initial filament linear density (dtex). The breaking force used is the breaking force - a continuous measurement experiment '//; ·. / 7 + · _; . / 7 /: '· / ..; ·> .. / · - //.-··'·/,. // 7'7 / 5 -, + .-'-'y ·, 7. / 5 - A.5 ;; // '. , 5 / · '. // / -7 .5 / '/7/./. 1 '' · maximum value of force.

The elongation at fracture E _H was calculated from. The ratio of equation 4 as the change in length delta ⁴ 1 to the initial length I of the sample when the breaking force is reached:

, E _H = delta I * 100% / I _v (equation 4), where delta I is the difference in sample length under the breaking force F _H and I _v is the initial sample length.

.

In the course of these studies, fracture force-elongation-flow diagrams were drawn together.

The defects in the thread were determined by Lindly Standard

Yarn Inspector (Series 1900) at 600 m / min.

The degree of textured: thread 7 / putlUmO / 7 // was determined in accordance with DIN 53 840. -7 - //,

35 / / -7'15: / The foam stability of the textured yarn was determined

.. / according to DIN 53 840. · 7 ^; '. Small angle radiography (RKWS) was used to study 5 cases. of which the twisted yarn is selected. morphology of samples. RKWS tests were conducted using a Kiessig low vacuum detector. The diameter of the 'collimator damper was 0.4 to 0.3 mm and the distance A between the' specimen and the photo plate (AGFA-GEVAERT, Osray M3) was 10 400 mm. With a graphite monochromatic filter, an emitter beam of 37 kV and 36 mA capacity (wavelength λ = 0.15418 nm) was obtained. For RKWS studies, POY threads were wound on a frame so as to accurately maintain the alignment of the individual filaments. From 0.7 to '1 mm ·, the beam of fiber was' irradiated perpendicular to the X-rays by the vertical axis of the fibers. The exposure time was 20 or 40 hours.

From crystalline-amorphous POY fiber regions on. The meridian reflexes formed on the RKWS photographic plate were evaluated using a photometer (3CS microdensitometer, Joyce Loebl), using a gray scale of ru black degree D = 0.95. The resulting half-width of the resulting photometric curve is the value expressing the thickness of the crystalline -fibrils perpendicular to the fiber axis. The lateral crystal thickness # can be approximated as follows:

# = λ (nm) / B (rad) (Equation 5), where λ is the X-ray wavelength, Birad) is the half width of the photometric curve measured in units of the arc. B (rad) is calculated from Equation 1 6:

B (rad) = B (mm) / A * F (Equation 6),

¹⁶ ;

. where A is the distance between the beam sample and the photo plate, F is the photometer transfer factor. When A = 4O0 mm and F = 5, equation 5 transforms into equation 7:

M 1 (nm) / B (mm) J * 2 * 103; (Equation 7).

⁵ .

Polycaprolactam is melted during spinning. extruder (Barmag 3E-24S, 38 mm diameter mandrel, L / D = 24) and extruded through a 12-hole die (0.2 mm diameter, 0.4 mm capillary). The resulting strands 10 are initially routed through an inflatable shaft (height ^-

1600 mm, transverse purge with air at 22 ° C and 65% relative humidity at a velocity of 0.4 m / s), then passed through a 2000 mm high shaft to a test spinning site (Firm EMS-Inventa) through two 150 mm diameter spinning . discs and wrapping - in a reeling machine (Barmag SW 46 1S-900). '

The distance between the nozzle and the grafting machine was 1300 mm. .

The tensioning was carried out in a cold manner on a tension-torsion machine at 740 m / min (J5 / 10a, Rieter).

The stretching-texturizing was done-stretching25 on a texturing machine Barmag FK6L-10 at speeds from 600 to 800 m / min.

A. POLYCAPROLACTAM SYNTHESIS

EXAMPLE 1

Melted 0,5% by weight of water and 0,53% by weight, -. 7; · - '··· Caprolactam containing terephthalic acid as a chain regulator was introduced into

The first reaction zone of the VC-reactor at the desired pressure. The flow rate was 25 kg / h. At the same time. during the first

A mixture of 70 wt% polycaprolactam (RV = 1.9) and 30 wt% titanium dioxide (Anat-Modification) was introduced into the LT308TB .17 'polymerization zone at 225 g / h. -The temperature of the first reaction zone was 252 ° C. In the subsequent zones, the excess polymerization heat reaction internally was removed by cooling the heat exchangers. The temperature of the last reaction zone reached 265 ° C.

After extraction with boiling water and drying, the polymerization product had relative viscosity

2.39, 36 mMol / kg of chemically bound terephthalic acid and 0.3% by weight of titanium dioxide and 0.046% by weight of moisture. The elastic elasticity J _e was 8.3.10 ⁶ .Pa * ¹ , its relative unit R = 0.78.

EXAMPLE

Caprolactam was polymerized with '0, -80% by weight of 20-terephthalic acid as' chain regulator under the conditions described in 1. in the example. The polymerization flow rate was 30 kg / h and the titanium dioxide mixture was introduced at 270. g / h. - Other experimental conditions were maintained as in Example 1.

The product had a viscosity of 2.32 and contained 54 mMol / kg of chemically bound terephthalic acid. The elastic elasticity J _e was 5.1.10 ^-6 Pa ^-1 and R = 0.48. The titanium dioxide content was 0.3 wt% and the residual moisture was 0.016 wt%.

EXAMPLE. "

Caprolactam containing 0.7% w / w water was polymerized at 30 kPa with 0.21% w / w terephthalic acid as a chain regulator.

The polymerization flow rate was 34 'kg / h. The temperature of the first reaction zone was <240 ° C. Titanium dioxide was not added during the polymerization.

The product had a relative viscosity of 2.71 and contained 5 "14mMol / kg of chemically bound terephthalic acid.

-The residual moisture content was 0.019% by weight.

EXAMPLE conditions,

The first

0.6% by weight of water-containing caprolactam was polymerized using 0.29% by weight of terephthalic acid as analogs of a chain regulator. The reaction zone temperature was 245 ° C. Other experimental conditions are maintained as in Example 3. 'During the polymerization, titanium dioxide was not added to,

The product had a relative viscosity of 2.71 and contained 19 mMol / kg of chemically bound terephthalic acid. The residual moisture content was 0, /) 21% by weight.

EXAMPLE 5a

The polymer was acidified as a chain at a temperature of 251 ° C with 0.6 weight polymerization.

; water-containing caprolactam was present in the presence of 0.37% thick terephthalate regulator in Example 3 First reaction zones Other experimental conditions were maintained as in Example 3. No titanium dioxide was added.

The relative viscosity of the product was 2, ^67/7 he was 25 mMolZkg / chemically bound terephthalic acid. / + Moisture content: - <S Dare; / Q ', H91: ⁷ svprro / ^7%. /. /

. ¹⁹ ····

EXAMPLE 5b.

, Caprolactam containing 0.5% by weight of water was polymerized in the presence of 0.26% by weight of adipic acid as a chain regulator under analogous conditions to Example 3. The polymerization flow rate was 35 kg / h. The temperature of the first reaction zone was 250 ° C. Titanium dioxide additives were not present.

The product had a relative viscosity of 2.67 and contained 20 mMol / kg of chemically bound adipic acid. The moisture content was 0.018% by weight.

EXAMPLE 5c

0.5% water-containing caprolactam was polymerized in the presence of 0 to 81% by weight of lithium salt of 5-sulfoisophthalic acid as a chain regulator and 0.18% by weight of titanium dioxide. After extraction with boiling water and subsequent drying, the product had a relative viscosity of 2-55, containing 0.20% by weight of titanium dioxide. The moisture content was 0/031% by weight.

8. QUICK SPINNING OF POLICAPROLACTAM

EXAMPLE

The polycaprolactam produced as described in Example 1 was spun at a melt temperature of 265 ° C and (a) 4500 m / min or (b) 5500 m / min. The RV for the yarn was 2.48. The resulting filaments had a linear density of (a) dtex 50 f 12 and (b) dtex 41 f 12, the titer of the spun at 4500 m / min and then the stretched fiber was dtex 44 'f 12.

The results of the experiments are shown in Table 1.

/ 7 /. '' ·· -: '1 / - .. (' <- / - ^ / (/ 77 / + 7/7 '<77 /' 20 ((/ 777 / '7? 77- / -7?: 7.777-7 /((-..- 1 / COMPARATIVE EXAMPLE The test in the example was repeated with commercial polycaprolactam (chain regulator:

(. ..... 7: / {(/ 7 (7 · .. .. (7 / 77.7 ''

5 'propionic acid in product = 40 mMol / kg; RV = 2.37; titanium dioxide content = 0.3% by weight;

elastic flexibility 11.5. 10 ' ⁶ Pa'¹; moisture content

0, 044% by weight). Other conditions were maintained the same.

The results of the experiment are shown in Table 1.

EXAMPLE

15, - The polycaprolactam produced as described in Example 2 was spun at a melt temperature of 265 ° C at (a) 5500 rpm and (b) 6000 m / min. Fiber RV = 2.31. The twisted filaments had a linear density of (a) dtex 42 f and 12 (b) dtex 43 f 12. '

The results of the experiment are shown in Table 2.

COMPARATIVE ,, EXAMPLE

The assay described in Example 7 was repeated with commercial polycaprolactam as described in Comparative Example 1. Other conditions were maintained the same.

The results are shown in Table 2.

EXAMPLE

Polycaprolactam (7) was prepared according to the description of Example 3 at a spin speed (w / w t / 2.75 ° C (tpm), (b) 5500 m / min and (c) 6000 m / min. , 79 The linear densities of the twisted filaments were (a) dtex 54

Υγ ′ Y 21 f 12, (b) dtex 51 f 12, and (c) dtex 52 f 12. The titer of the thread after the passage was dtex 45 f 12, the spinning rate.

- 4500 m / min.

The results are shown in Table 3.

COMPARATIVE EXAMPLE The test described in the example was repeated with commercial polycaprolactam (chain regulator; propionic acid in product = 20 mMol / kg; RV = 2.68; elastic elasticity 10.0.10 ^-6 Pa '¹; moisture content 0.012% by weight). Other conditions remained the same. '.

The results are shown in Table 3.

EXAMPLE

Polycaprolactam produced according to the description of Example 4 was spun at a melt temperature of 275 ° C at 4500 m / min. The fiber RV was 2.83, resulting in a filament titer

- dtex 54 f 12. 'After that the fiber was. stretchedtextured extrasensory. machine (firm Barmag FK 6L-10) at a speed of 600 m / min at 180 ° C at a D: Y ratio of '~ 2.33 (ring combination and order: Ceratex ceramic rings arranged in order 1-5-1); .such a textured yarn was obtained.

The results are shown in Table 4.

COMPARATIVE EXAMPLE The test described in the example buco was repeated with the commercialization described in Comparative Example 3.

polycaprolactam (moisture content 0.017% by weight). Other conditions are maintained.

The results are shown in Table 4.

5 £ ^ 33333 / || 333 <33ΐ3 ^

EXAMPLE

Polycaprolactam produced according to the description of Example 5a was spun at 275 ° C. At 5500 m / min, the Fiber RV was 2.69. The titre of the twisted filaments was dtex 54 f 12.

The results are shown in Table 5.

COMPARATIVE EXAMPLE ”The test described in Example 10 was commercially available polycaprolactam (chain propionic acid in product = 20 mMol / kg; RV = 2.66; elastic elasticity 10.0.10 ^-6 Pa- ¹ ; moisture content 0, 098% by weight, ⁵ %) ). Other conditions were maintained the same.

repeated with regulator r

The results are shown in Example 5.

syyyyBy 3 .. 3. · '...

EXAMPLE

Similarly, polycaprolactam (0.37% w / w as a chain regulator, relative viscosity 2.67, · content of chemically bound terephthalic acid in the final product at 25 mMol / kg, moisture content 0/02% w / w) prepared according to Example 5a was spun. at 275 ^U C at 4500 m / min. The fiber RV was 2.78. The spinning titer was dtex 54 f 12. The fiber was then stretch-textured in a press-texturing machine (firm Barmag, FK6L-10) at 800 m / min at 180 ° C.

·. . ²³ · i temperatures at ring combination Ceratex 1-5-1 and 'Y' D: γ Y ratio 2.2. - Y / to.

The results are shown in Table 6

COMPARATIVE EXAMPLE,. <The test described in Example 11 was repeated with commercial Ypolicprolactam (chain regulator:

propionic acid in the product = 20 mMol / kg; RV = 2.68; moisture content 0,017% by weight (. Other conditions maintained _; Y

The results are shown in Table 6.

COMPARATIVE EXAMPLE (analogous to DE-A 40 19 780) Polycaprolactam synthesized according to Example 4 of DE-A 40 19 780 (relative viscosity 2.36, titanium dioxide content 0.03% by weight, moisture content 0.04% by weight) was melted in an extruder (Barmag 3E, '3-zone earthworm, 30 mm cross section with low temperature mixing section (L / D - 24) at 269 ° C, and pressed through the following parameter nozzle (13 holes, hole diameter 0.20 mm, capillary length) 0.40 mm) The fiber was then cooled with air at 24 ° C and 40 · ..% relative humidity in a blast shaft (1500 mm length with transverse blast), passed through a 2200 mm free fall shaft and wound.

The wrapping was 'on the Barmag- (SW46 SSD) wrapper at a speed of 4250 -m / min' ·. The filament titer was dtex -56 f 13.

The distance between the nozzle and the recess was 1300 mm. y '/,' - · '<

The stretching was carried out in a cold-way tensile-rotating machine (Rieter J5 / 10a) at speeds of 605 m / min to a tensile fiber titer of dtex 44 f 13.

, ..... 4.

The results are shown in Table 7

COMPARATIVE EXAMPLE 8 The test described in Comparative Example 7 was repeated ^v 10 with commercial polycaprolactam (chain regulator: propionic acid in product = 40 mMol / kg; titanium dioxide content 0.03%, moisture content 0.04% by weight). · Other conditions remained the same.

EXAMPLE '12

Polycaprolactam produced according to the description of Example 5b was spun at 275 ° C at (a) ^ 4500 m / min, (b) 5500 m / min, (c) 6000 m / min. The fiber RV stood at 2.78. The titre of the twisted filaments was (a) dtex '53 f 12, (b) dtex 53 f 12, and (c) dtex 54 f 12. The titer of the' 4500 m / min spun and then stretched 'yarn was dtex 44 f 12.

The results are shown in Table 8.

EXAMPLE

Polycaprolactam produced according to the description of Example 5c was spun at a melt temperature of 275 ° C at (a) 4500 m / min, (b) 5500 m / min, and (c) 600 m / min. The fiber RV stood at 2.75. The spinning titre was. dtex 54 f 12, (b) dtex 54 f 12, and (c) dtex 55 f 12.

The titre of the yarn spun at 4500 m / min and then stretched was dtex 44 f 12..

The results are shown in Table 8.

COMPARATIVE EXAMPLE S / and the test described in Example 13 was repeated with commercial polycaprolactam (chain regulator: propionic acid in product = 20 mMol / kg; RV = 2.72; moisture content 0.033% w / w). Other conditions remained the same.

The results are presented in Table 8, Table: Example 6 and Comparative Example 1

Example 6 1 paly ~ '. example 7 / (a) 77 1B) 7 // <W (a) 7 // (b) Molding speed in m / min 4500 5500 4500 5500 K) Specific tensile strength cN / dtex of Y (twisted spun yarns) 7 //: <577 iOO ·; iWO / 4.2 Break Elongation% 7 / ^: '5.7.7 // '1753 (7). '7 / SS' / 7 ' 54 Specific tensile strength of stretched yarns CN / dtex 4.8 4.6 Break Elongation% 38 7 /// 7/7 // Pratanpa defects / lOOkg 0.3 1.0 Throw defects / lOOkm 0.02 '0.03

The data in Example 1 shows that 'the specific breaking force of the formed fiber is' higher and that fewer defects occur during fiber processing than in Comparative Example 1.

Table 7: Example 7 and Comparative Example 2

Example 7 2 Comparison example (b) R / «B / ft>) Molding speed in m / min // Or 6000 5500 6000 - POY (specific tensile strength cN / dtex for untwisted spun yarns) '· 4.8 4.8 4.2 4.4 Break Elongation% //// 55: //// B / ol / i .50 Lateral crystal diameter [rmf //// ^ 0 - /// 9.4

In these examples, the breaking strength of POY yarns is 9-14% greater than that of conventional ^ yarns.

· Table 3: Example 8 and Comparative Example 3

Example 8 3 Comparison example (a) SiB (c) (a) / B; (c) Formation speed m / min 4500 5500 6000 4500 / SsoO / 6000 / '//; / - -. "./ / & '/' /., '' EOY (spun loose yarn) specific breaking force cN / dtex 4.19 // '/// 7 /// #'. 4.43 // 3> Ο // 3Wi '3.75 Break Elongation% : /: 72 // / M: / 56 //: 75 //  66 to 59 Lateral crystal diameter [nnj 9.1 10.5 Specific tensile strength of stretched yarn N / dtex 4.73 ///// 7 4.38 Break Elongation% 39 38

These examples show that the yarns (POY) produced according to the invention have a specific breaking force of 3-18% higher than that of the comparative test yarns, even at relatively low levels of dicarboxylic acids. At a forming speed of 6000 m / min, this size grows.

/ <Υ'7 / 27'.7 '\

Table 4 /: Example 9 and Comparative Example 4

Example 9 4 Comparison example POY (twisted untwisted yarn) specific breaking force in chN / dtex ·? '-' 77 // 7.74, · 45- 3.79 Break Elongation% 7? /// 77Υ70 / γ7 ^; > γγ b // ?: / 'ΥδΥ /////? Extended-textured yarn Pratanpa ratio. ? /Y / Y to: 25, / '77 / 7 · 1: 1.31 The titre dtex ./?'//?45 ' _: f / 12; //// Y; 43 f 12 Specific breaking force cN / dtex ; Y? 7/22 |? 4? 87: i; - 'f /.;. ^7th 4.4 Break Elongation% 29th 29th Foaming degree E% 56 59 Foam size K% 43 ' 41 Foaming stability B% 84 77

In this example, the specific tensile strength of 5 unstressed yarns (POY) produced in accordance with Fig. 7 is 19% and that of the stretched textured yarns is 9 *% higher than that of the reference sample. The foam stability of the polycaprolactam yarns produced according to the invention is also significantly increased.

.

Table 10: Example 10 and Comparative Example 5

Example 10 5 Comparison example POY specific twist force cN / dtex / '/ 77;? I'l / ^; 9 / l? 77'7 ·:?) Break Elongation% χ / 7γΐ753, · 9 /? 77'7)? 77 55.5

This example shows an excellent breaking strength of the yarns of the invention compared to standard yarns. From the data presented, we can see that the resulting POY yarn is unusually high. an elongated combination of strength and low fracture. After twisting the thread, the extension has decreased -a POY yarn to an unusual size. This indicates the suitability of the yarns of the invention to be 'direct'

for use? ie without extra tension like PO Y ^{, r} 3 ^ ady to ūse 'f'as spun).

Table 11: Example 11 and € comparative example

- r— · ................................. Example 11 Color example ΕΌΥ specific tensile strength d </ dtex of the twisted untensioned yarn • 4.27 3.79 Elongated% 66 78 Lateral crystal stroke [cnj 7? 7 10.5 Thread-textured yarn Pratelpa® Ratio. ; 1: 1.25 1: 1.31 Caption cte: 45 f 12 43 f 12 Specific drag force cN / dtex 4.9 4, 36 Break elongation% ® 30th 29th Blowing degree E% 57 ' 58 · ' Foam size K% 40 39 Foamy Sphincter®s B% ' 84 ' 76

We can see from the example of 'Ii ©? that - f> the specific tensile strength of the retracted-textured yarns is '12% greater than that of the comparative yarns. Stability of foaming is. increased by S% and indicates the suitability of yarns made 'according to the invention'; stretch-texturing - ¹ at - high, at> os-texturing speeds.

Table: 7 and ® comparative 'examples

o '7 comparisons 8 gals example ΣΌΥ specific tensile strength cN / dtex of twisted untwisted yarns '4.43. ' . 4.31 Missing? ® extended% '', '. ^: 68, 68 Is the 'specific' rupture cR / dtes of stretched yarns? ^; '  4.95 '' * 4, 98 Elongation at break%; 35 34 Bratasapos de £ ekfcai / lQQkg . 1? 1 0 Throwing cte £ ects / 10G km 0.31 0.17

The following comparative examples show that for a product made with dicarboxylic acid (Comparative 7), at a forming speed of 4250 m / min and RV 2.36, POY 7 yarn. the specific breaking force is only 2.8% better than that of the product made with monocarboxylic acid. This is still within / analytical confidence limits. Pratempto fibers, a 'do not see any / improvement, as compared with conventional technique ^7: 7 / level / 7 product 7 (cf. 8. Example).

· · Table: Examples 12, 13 / and Comparative Example 9 // -, - / 7 '77 //; - //

Example 12 Example 13 · 9 Comparison example (a) /. (b) ic) (a) (b) (c) (a) • (b) (c) Molding / Speed [m / min] 4500 5500 6000 4500: :: 5500, '6000' 45a0. 5500 6000 POY (spun unstretched yarn) specific to rupture force [cN / dtex] 4.6 4.6 4.7 4.8 4.8 4.8 / 4.17 4.2 4.1 Elongation at break [%] // - 70 / 61 54. 68 59 - / 54/7 7 - '77 '' '' / '657j 60 Specific to the yarns used breaking force [cN / dtex] 7,5,3. ' 5.5 '-.' 7-7'7 4.9 / // - 7- Elongation at break [%], 39 39 / 740 // ....

This example shows that the specific tensile strength of unstretched yarn (POY) and stretched yarn produced according to the invention is 8-17% higher than that produced by modern standard techniques.

Claims (4)

DEFINITION OF INVENTION 1. Polyvaprolactam-based filaments with a relative viscosity RV of 2.0 to 3.0 (measured at Ig filaments 5 .. at a concentration of 100 ml of 96% sulfuric acid), characterized in that the melt consisting mainly of polycaprolactam is extruded through a die to produce polycaprolactam filaments, thereby cooling and removing at least 10 3600 + 1250. (3.0-RV) m / min, whereby the spinning polycaproactam is synthesized in the presence of at least one dicarboxylic acid selected from the following groups of organic acids: C ₄ -C 15 _i0 -alkandikarboninių acids -C ₅ -C ₆ -cycloalkandicarboxylic acids; j benzene and naphthalene dicarboxylic acids capable of 20 have up to 2 sulfuric acid groups with molecules V carboxyl groups are not contiguous; -NC ₁ -C 1-6 alkyl ~ N, N-di (C ₄ -C ₁₀ alkanecarboxylic acid) amines; -1,4-piperazine-di (C 1 -C 4 -alkanecarboxylic acids). 2. A method of making polycaprolactam yarns according to claim 1, characterized in that The polycaprolactartine used in spinning is synthesized in the presence of at least one N, N-di (C ₁ -C ₈ alkyl) amino (C ₂ -C ₁₂ alkyl) amine. . .K · 3. A method of making polycaprolactam yarns according to 35, wherein the polycaprolactam is used in spinning to synthesize into /,.,. 31 '' in the presence of one primary C 1 -C ₁₂ -alkylamine or G ₆ ('aryl-C 1 -C 4 -alkylamine i.'. I / -; lj 4. A yarn obtained by a process as set forth in claims 1 to 3, characterized in that its length does not exceed 100%. 5. Use of the yarns referred to in point 4 in the manufacture of fibrous materials and textile products.