DE1694476A1 - polyamide - Google Patents

Description

DR .-) NQ. H. FINOKE ^β ^ Γ ^ Γ «" ¹ ItLMOV.

DIPlI.-INQ. H. BOHR DIPL / -ING. S. STAEQER

Fcrnrufi * 2 < <· <0

1694A76

Folder 21456 Case FG ₀ 19752

Description of the patent application for the

Imperial Chemical Industries, Ltd., London, Great Britain

regarding "polyamide"

Priority: November 10, 1966

Advertising, the invention relates to the production of polyamides and made therefrom yarns, in particular yarns which contain by melt spinning of polyamides, the finely divided inorganic nucleating agent, manufactured *

the,

In the German patent specification ..., (file number J 31 763) it was stated that by dio ßinarba5.tung gewtaoer or? A-

-2-BATH ORIGINAL

nischer nucleating agents, preferably polyaeric nucleating agents, unstretched unstretched in polyamides Threads can be obtained, the defined X-ray parameters have »which parameters as the difference between the orientation factor 0. and 0 of the just spun threads are expressed. So 0. - 0 should be greater than 0.2. By melt-spinning oleulants containing polyamides in threads with the above-mentioned Rönigenebrahlenparaineter and through subsequent Orientation of the threads by conventional drawing processes a significant increase in productivity is achieved in spinning. This can increase productivity expressed as productivity ratio (P.V.), which is defined as follows:

Draw ratio "which results in a 30% hot elongation in a yarn containing a nucleating agent

Draw ratio, which is a 30 # length elongation at break in the case of one that does not contain any liucleating agent Thread yields

The PV is only used as a measure of the increase in productivity in processes with high spinning speeds, doh. in processes using speeds above about 610 m / min. In processes b where normally low Cpinngesohwindigkeiten, d, h _o be approximately 457 m / min or less is used, is -11 "

BATH ORIGINAL

l; U 9 tf »·> '■■■' \»

Increase in productivity due to the solubility of the increase the flow speeds achieved.

It has also been found that certain inorganic materials They can also be used as wrapping agents in polyamides and in undrawn silk-spun Threads that have the X-ray parameters given above ergebon ^ 'being a similar increase in Productivity is achieved «Ss was found further, AaB the incorporation of these hoeing agents to thread with leads to an improved quality, for example a yarn with a more uniform denier and with more uniform Coloring properties. can be obtained over the entire length.

Finally, it was also found that the particle spacing of the nucleating agent in the polyamide is an important criterion with regard to achieving uniform nucleation of the polyamide with inorganic nucleating agents. Thus is achieved with nylon ~ 6 _f 6 over a wide range of spinning speeds an effective nucleation when the average spacing of the particles of the NukleierungsBittels in the polyamide, hereinafter referred to the average Mukleierungsmittelteilchenabstand _r less than 1 i ^ istr an even more advantageous nucleation is obtained if the average nucleus

BAD 0RieiNAU4- 009843/1905

ierungsmittelteilchenabstand small as 0.5 M * - _o Unless otherwise indicated, relate to those indicated in the sequence Nukleierungsmittelteilchenabstände values calculated from the concentration by weight of the nucleating agent in the polyamide and the average diameter of Hukleierungsmittelteilchen used in the preparation of the nucleated polyamide The mean diameter of the nucleating agent particles, for example in an aqueous suspension, can be measured using an electron microscope at a magnification of 99,000 times. At this magnification corresponds to 1 cm 0.1 u ,, so that for example with a centimeter ruler, the size of each particle can be easily auegemessen to 0.005 AU ₀ Sin sweckmäßiges method is to photograph a dilute suspension of the particles and then the size of each Measure the particle in the photograph, from which the mean diameter of the particle can be calculated

The average nucleation center pitch in the polyamide obtained in the above manner agrees well with the value obtained by direct testing of cross sections of nucleated yarns is obtained using the electron microscope.

0098A3 / 1905

Am factor that determines the nucleating agent particle distance the achievement of an effective nucleation is influenced, the KristaUlsationsgeschwindigkelt of the polyamide, and the maximum nucleating agent particle distance can be used as a function according to the rate of crystallization of the polyamide the following theory can be printed out »

Freshly spun filaments obtained by melt extrusion of a Polyamides usually solidify rapidly on cooling to a non-crystalline, supercooled, glassy structure, the solidification point being somewhat arbitrary and referred to as the point in which a constant titer is obtained in the cooling zone o With this type and method of cooling, the solidification of the polyamide can be influenced noticeably by external cores, which are generally known gloss effects in the spun threads and variable properties can cause «. It has been found that the addition of a finely divided inorganic crystallization nucleating agent in sufficient quantity both increases and stabilizes the solidification point of the threads just spun by solidification can be-,

009843 / I: JQ5

When the freshly extruded thread cools below the melting point »then the crystal fronts move forward from the crystallization nuclei at a speed» which depends on the temperature »and. if the crystal areas of neighboring cores, which are separated from one another by an average distance S, »meet» then the polymer is solidified »so that the addition of an inorganic nucleating agent is effective» sufficient cores must be present to give the yarn a linear crystal growth before the filament is quenched to a glassy state. The required concentration of inorganic "nucleating agents" for a given particle size can be determined when the maximum spherulite size is used in a high speed spinning process using a polymer. Has been incorporated into the no nucleating agent is known »This maximum spherulite can be calculated from the measured Sphärolithwachstumsgeschwindigkeiten as a function of temperature and tent-temperature Zusamiaenhangs ä & r threads measured in spinning" Thus the Sphürolithradlus by numerical integration of the expression (G (T ) dt calculated »where Cl (T) is the spherulite waist velocity at temperature T. The integration is carried out between the spinneret plate and the process, which also defines the point Int, bßL Λ au ^ in remain-

0 0 9 8 4 J / I U 0 ^

BATH ORIGINAL

the titer in the cooling zone is reached and which is the ue experimental pull-down curves from the relevant Polyaeid spun threads is determined.

The amount of inorganic nucleating agent that is required to achieve the desired effect can therefore be defined with the maximum distance between the individual inorganic nuclei, so the mail is mule Nucleating agent particle region 3 in which solidification by crystallization occurs earlier than

Solidification through hypothermia, through expression

(JC 8 ^ 2 1 G.dt given, wherein t the tent of the spinndU-

* 0 sen plate and XC is the distance from the spinneret plate dee unnucleated solidification point when melt spinning in threads is. "

The above expression is used to estimate the mean maximum nucleation age distance for nylon-6,6 spun at two different spinning speeds, where the equation ₀ β (Τ) - 2.63 -

is used to calculate the spherulite average speed Q (I), where G is expressed in m. per lake and T in ⁰ O ο The above equation is derived from the equation of

009843/1905

. Hagill, Polytoer, Volume 6, July 1965, page 367. The bristles of the two different Spimrrereuohe are given in the following table

On winding speed m / min

Titer of Bponnenen dens in the

Calculated spherulite radius B / 2

Vucleation «ittelabetajri 8

1341 268

11th 62

0.65

Juu

Ο, θβ jLo 1.30 m.

The results suggest that within this range of spinning conditions at Iylon-6.6 the cladding part a distance of about 1M. or should have less, what good old the experimental given below Numbers match and what also applies to other polyamides, the rate of crystallization is the same On the order of ffylon-6.6.

Thus, according to the invention, a polyamide is proposed, which contains a finely divided, inorganic "covering agent" bit less than 0.5 m in diameter, the aaxlaale alt animals distance between the individual particles of the named coagulant due to the external pressure

2 0

■ Cr a CL Xl

BATH ORIGINAL

009843/1905

169U76

is given, where S is the mean distance between the nucleating agents, G is the rate of crystallization of the polyamide, and XC is the distance from the spinneret plate to the solidification point of the un-nucleated polyamide when spun into threads.

For nylon-6,6 and other polyamides with crystallization rates of a similar order of magnitude, the mean distance between the nucleating agent particles is preferably less than \ u, and in particular less than 0.514, »

Filaments spun from the above polymer are normally then subjected to a cold drawing process in order to achieve molecular orientation. Certain difficulties may be encountered during this stretching process, and it is therefore preferred that the polymer contain at least 0.03 wt% -5S of a matting agent to facilitate cold stretching. At least 0.2 wt% matting agent such as TiO ₂ should be added to achieve a significant degree of matting «.

It is preferred to use polyhexamethylene adipamide, but other polyamides with overall crystallization rates

-10-009843 / 1905

~ ίο -

in the same order of magnitude as nylon-6,6, as s.B. Polyoctamethylene adipamide and folydecamethylene adipaaid, can can also be used successfully

The most preferred organic detergent is calcium » fluoride (CaFp) * Other also effective inorganic Nucleating agents are: talc, pyrophyllite, agallth, "Asbentine, antimony trioxide, molybdenum disulfide, grafbit or Lead tungstate. .

According to the invention, a yarn is also proposed, which contains at least one undrawn polyamide thread, that produced by melt spinning the polymer defined above and has a molecular orientation that gives an X-ray reflection adiaee, where Oi - 0 is greater than 0.2 c Varzaga-wise is 0. ^ bigger than nail,

0. and 0 are calculated from measurements made with the large-angled SötttgeiiBrahlen-Laue-Diajpramni, that of the threads is obtained, made ^

The Laue diagram showing the fiber has two main rings, an inner and an outer ring, which reflections from the paratropic main grids of the crystal structure

BAD ORIGINAL-11-00984 3/1 9OB ^ ^-

1694478

Tür sludc The intensity of these rings (M) on the meridian ~ the meridian eats a straight line on the X-ray film, which runs parallel to the fiber redirection and through the location of the primary X-ray beam - and (B) on the equator - the Xquator is a straight line the X-ray film, which runs perpendicular to the direction of the fibers and runs through the log of the primary X-ray beam - can definitely earth, and orientation factors jjg | can be calculated "earth" For the sake of convenience, "earth" the orientation factors for the inner ring with O ₁ and tVüf denotes the outer ring alt 0 _Q.

The values for O ^ and 0 _Q «are determined in the following Velae«

The yarn sample is placed as a parallel fiber bundle on one a simple sample holder, which is then brought into an evacuable X-ray camera, in such a way that Bundle perpendicular to the primary X-ray; is-ray lies. Am· flat film plate becomes the primary beam and bank right on the belt opposite the X-ray source « of the fibers arranged so that he has the diffraction diagram of the Fibers can receive »The primary ray« ird ao gtfttbrtf that he has the file near the center In the usual Way cuts · The camera is during a minimal

RAn nnmiNAi 009843/1905

~ 12 -

Duration of 5 min (to a better * vacuum than 0.2 am Hg), and each sample is exposed for 15 min at 40 KT and 15 bA, the camera being continuously evacuated during the exposure. Hi-filtered Ou ₀ Ka, radiation from a closed X-ray tube is used, which is operated with a Phillip · PW 1008/30 generator.

The exposed film is as entwickeltι follows 5 a in Ilford PQX-1-ray film developer (at 20 ⁰ C), whereupon verification aneohliett a 30 Am or prolonged washing, u »maximum optical Diohte the film yon ersielen eu approximately 1.0 ·

Using a stepping Joyoe-Loebl double-beam microde bitometer (model B. 12 Hk * III), diametrical scans are carried out over the equator and the meridian. The two measurements ** would luf a "Director strip chart each superimposed auigesohrieben · J) 9r common ground will be charged before the intensity» »measurements (B or M) aft Xqvator Utod for at Meridian, the two main reflections are duiOhgefUhrt" The circumstances

»Earth dmim bestisMto

BATH

009843/1905

Finally, the invention also proposes a process for the production of a fine yarn which contains at least one drawn polyamide thread, as defined above, which is carried out by adding a finely divided inorganic nucleating agent with an average particle size of less to a polyamide incorporated as 0 _r 5 AL in a concentration sufficient to prepare a _r imkleiertes polyamide, in which the maximum mean distance between the individual nucleating '* mittelteilchen by the expression

S <2 G dt

f yes ** <2 I O

~ Yo

is given, where S is the mean distance of the nucleation - middle particle, 0 is the rate of crystallization of the polyamide, and XC is the distance from the spinneret plate up to the solidification point of the un-nucleated polyamide 1st, when this is melted into threads, and that the polyamide is furthermore present in molten form through at least one opening in a spinneret plate squeezes out.

Bas liuklelermittel can be used advantageously during the polymerization of the salt incorporated into the polyamide ., For example, a Caloiumfluoridbrel can be used

1 BAD ^ IJIAL [

003843/1905

The polymerization of Nylonsala can be injected into an autoclave, preferably during one . Period of 10-25 min at an autoclave temperature of 225 ° C and a pressure of 17.5 at. On the other hand, the calcium fluoride paste can also be injected into the spiral of a continuous polymerisation device . preferably at a point after 60 $ S the length of the evaporator section. The nucleating agent can be used in situ (for example using calcium adipate and hexamethylenediammonium dihydrofluoride) are produced in the "autoclave or spiral polymerization process" The nucleating agent can also be incorporated into the polyamide by means of a cut-off seal with an aqueous paste will"

The inorganic Nukleierungämittel must be in a finely divided state, _e h * that they have an average diameter of less "1" 0.5 ^. The average should preferably be smaller than OJAc and in particular smaller than ₀

The weight conistotation of the organism to be used Miiklei 'Taiigsmitteis in the polyamide depends on the part height

BAD ORI

RIGINAL

169 * 471

size of the material and should be chosen in such a way that that the maximum nucleating agent was not found Goes beyond the value, which by the Auadröck 2 j O dt. given let.

The effective nucleation of nylon-6,6 is achieved by using only 0.008 wt% calcium fluoride with a duroh ~ average particle size of 0.03 / t, achieved, but united more effective labeling is achieved if the tion of this nucleating agent is at least 0.06 amounts to. These percentages by weight of calcium fluoride correspond to an average adhesive particle distance of 1 K. 0.5Lc

The preferred inorganic nucleating agent, Calei 'fluoride, can be kept in a suitable fine particle size by the well-known method. . double conversion of a suitable calcium emulsion or a suitable fluoride! «in aqueous solution. For example, solutions of calcium acetate and fluoride fluoride are mixed at or near the boiling point, whereupon the calcium fluoride is filtered off or separated by centrifugation. It changes the particle size of the calcium fluoride obtained by this process with the ambient temperature «· So Toe * 6O ⁰ O becomes one

BATH ORIGINAL ί 009843/1905 14

in the range from 0.01 to 0.1 U / and at ICX) ⁰ C in a range from 0.05 to 0.5 U, obtained »

An advantageous method is, for example, potassium hydroxide and hydrofluoric acid or calcium adipate and hexamethylenedlamine-hydrofluoride in solution to implement, since the by-product serves to convert water or, nylon salt are.

The invention is explained in more detail by the following examples o In these examples are the concentrations Expressed in weight unless otherwise specified

example 1

(a) Manufacture of nuclear a.l ertea polyaer

348 g of fluoride were dissolved in 8 l of distilled water at the boiling point, and a solution of 474 g of calcium acetate in 8 l of distilled water was prepared in a similar manner. The two solutions were mixed slightly below the boiling point and stirred for a few minutes. The Gemisoh was then boiled YZ hour and finally on Naoht left. The clear supernatant layer, which was approximately 4/5 of the total volume, was decanted off and the remaining calcium fluoride was blown at 4000 rpm for 10 minutes

009843/1905 ^ßAD

centrifuged ,, The clear supernatant layer which constituted about 3/4 of the volume of centrifuged en suspension was then decanted from the centrifuge tubes _o

Finally, the aqueous paste containing 60% calcium fluoride was coated onto nylon 6,6 chips with the addition of pigment nylon in a Gardner mixer so that the final polymer contained 1,2% calcium fluoride _{or the like}

(b) Spinning and stretching processes

Construction polymer was in a Sohneokend: cuckschmel8er melted at a NND Spinngeschwixdigkeit of 1198 m / min and at a spinning temperature of 29o C ⁰ in a 13-spun yarn filamentous

In order to obtain comparative information in this and in the following examples, a control yarn was shown under spun and wound up under identical conditions of speed and temperature, using a polymer, that contained no added calcium fluoride, but otherwise possessed the same properties »

Both yarns were drawn at a drawing speed of Drawn 460 m / min, and the draw ratios were increased

009843/1905

»18 -

adjusted for each Qara so that a yarn with a titer tone 40 den and with 0.4 Z twists per 25 mund with a normal elongation at break of JOfi was obtained _o

(c) Properties of the spun yarn

Control With calcium fluoride
nucleated 9.2 1U2 -0.64 0.05 -0.06 -0.41 0.02 0.46 223 237

liter per thread (den)

DXA freezing point ⁰ C

Draw ratio for a 30 # elongation at break 2.92

Productivity ratio - 1.33

The DTA solidification point is the solidification point of the spun Yarn sample measured by differential thermal analysis using the method described in U.S. Pat above-mentioned German patent is described.

Example 2 Manufactures 3λιπ /? dee nyiri.eierten Polymers

45 »3 kg nylon-6,6 (polyhexamethylene adipamide) polymer with a relative viscosity of 40 and a content of

"19-

039S43 / 1S05

, ₂ hurdle in a Gardner-Schneokeniaiacher 1.13 kg of pigment nylon mixed bowel 1.13 kg of a 0.4 # aqueous suspension of CaP ₂ mixed, ao that a GaP was obtained ₂ concentration in the polymer of 0.1% . The average particle size of the OaFp in the aqueous suspension was, Q3M # α

The calcium fluoride slurry was prepared as follows: 1055 g of calcium acetate (purity 91 $>) was dissolved in 3103 ml of demineralized water so that a saturated solution was obtained, and 760 g of potassium fluoride (94 # purity) was dissolved in 3103 ml of demineralized water Solutions were filtered, and the potassium fluoride solution was brought to the same volume as the Caloiuaaoe did solution. "The filtered solutions were then" separated at room temperature and at the same volume speeds with the aid of a micropump in the arms of a T-piece made of glass with 6 ^ 3 mm Inside diameter where the stoichiometrically balanced solutions reacted and calcium fluoride would precipitate The precipitate was pressed together with the aluminum acetate solution through the open end of the T-piece into a suitable container ο To increase the reaction speed, a stainless steel stirrer was inserted into the open end of the T- Piece into the reaction zone

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009843/1905

inserted and rotated at a speed of 1500 rpm ₀

The resulting suspension contained 500 g calcium fluoride with an average particle size of about 0.03 » measured with an electron microscope at 10,000 times magnificationο This suspension was thixotropicο

The gel suspension was diluted in order to achieve a final concentration of 0.6 # calcium fluoride by making up to 83 liters with demineralized water. The flooded potassium fluoride was allowed to settle for 4-6 hours and the supernatant clear liquid was siphoned off. The suspension was then diluted again to 0.6% , allowed to settle for 48-64 hours, and the clear supernatant liquid was decanted off, and further demineralized water was added so that a concentration of 0.6% was again achieved «

Spinning process

They were coated with CAFo Polymersöhnitzel at a polymer throughput of 3 _r 5 kg / at a speed of 680 m / min st spun in 12 monofilaments The yarns were quenched in the spinning chimney, and after a distance of 107 cm

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009843 / 190.5

~ 21 -

together of the spinneret plate using an Honofilspinnrohres, but wherein the spinning Central line was offset from the chimney ₀ The yarn was mm at a frequency of 700 cycles / using a crossbar hub of 58.7 wound min »wherein the trigger voltage is below 6 g / den by appropriately adjusting the rotation angle around the finish roller and the finish roller pins. Good biscuit constructions "which were independent of moisture content within the range of 1-13 $" were obtained The _{spin finish applied was thrown off o} This was eliminated by the use of a modified thread pull, whereby the threads were pinned over the godets in groups of 4 thread lines, each of which contained 5 threads, after the spin finish had been applied and then back into the individual threads at the splitter pin was separated

Streoktwistunft

The hono thread was drawn on a draw twister at a speed of 1280 m / min using a draw ratio of 4.71 to one liter of 15 denier. The drawn monofilament is wound up in yarn package with a long-short structure - rich chrome steel- ■ <.;. ■ *.: -? ΦΛ / ' ^ι: -rurcle used * der auf Eis «^ KU & erator W;

C w ί ί 4 j / Ί > j ö 5

12O ⁰ G heated «ar. The draw stick surface enteric, measured by a thermocouple, was 118 ° G, while the yarn temperature was at a distance of 25.4 mi bsw. 50.8 to unternai> of the pulling pins 94 ° C or "91 ⁰ C, the two Tenperaturmeseungen using Hastings-Raydiat-Tea ^ perature-measuring device was sitting was. . The relevant process data and yarn properties are given in Table 1 «,

Processing in hosiery

Six packages of twine weighing 1.36 kg, attached to the nucleated polymer that had been spun »were knitted into women's stockings. The stockings were both in appearance and also very satisfactory in use

Example 3

Example 2 was repeated, with the difference "that the Percentage of potassium fluoride was increased to £ 0.2 (0 »03yK, average particle size). The results of this Experiment are given in Table 1 «

Example 4 Example 3 was repeated, but the spinning speed

ir.Hten you 893 or 1198 m / mln was vervondet .. The Rasul- ' ■ _; ; - ο.; ·; · -ν; -ϊ; Y-Vr-.:;-)^ are iu Tp.oci; ..-? 1

BATH

Table 1

example 2 3 «- ■ 843 1198 Control
rereuoh Spinning speed 680 680 0.2 0.2 425 m / min 0.1 0.2 0.33 0.33 f » CaF ₂ 0.43 0.33 0.60 0.55 at the average hook
leierungarajttelpartchen-
distance (yM.) of the CaF ₂ 0.51 0.54 234 232 - «, 08 ⁰ I- ⁰ O 235 234 225 DTA solidification point ⁰ C

Example 5 Heratell ixntt of i! "V ^ eierte PoI

4153 kg of nylon-6,6-PolynerseJmitzel with a relative viscosity of 36 and a content of Q ₉ Jt XiO ₂ were coated with calcium chloride by being treated with a 59 (1 g * n aqueous dispersion of calcium fluoride (average high particle size 0.03 / o ) was mixed together with 1.13 kg of Pigaentnylon “QLe calcium fluoride concentration in the polymer was 0.09 £ _o

Spinning process

The polymer-coated chips were placed in a (came spun, the threads at a distance of 120 om

009843/1905

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were brought together by the spinneret plate and the The convergence point was 19 inches (50.8 cm) from the chimney,

V first triangle twist

The yarn was drawn on a stretch twister at a Veretreok speed of 1000 m / min and a Veretreek ratio of 4.00. A matt-finished steel Gift pen was used, which was ^{heated to 100 0} C ο Baa

the pre-stretched yarn had a linear density of 70 / and contained

20 threads. \

Process details and the yarn properties are given in Table 2 together with those of a comparative sample. specified »

Table 2

example 5 Comparative
sample Spinning speed m / min 1110 rtio CaF ₂ GeW ₉ - * 0.09 - average particle size of the 0.05 - average distance of the part
the GaF ₂ Ku ₀ ) 0.45 - Distribution ratio for a 50 #
Elongation at break 4.00 5.05 ⁰ I- ⁰ O 0.45 0.08 DTA solidification point ⁰ C 254 225 Productivity Ratio
O O O XU 3/1 OO G ' 1.52 UO

~ 25 -

The yarn spun from the nucleated polymer was bulked on a false twist crimping machine, and the bulked yarn was knitted into a fabric. Bas Comparative yarn spun from a polymer containing no calcium fluoride was used in the same Wisely puffed and transformed into a textile fabric · Da « nucleated yarn gave a satisfactory bulk behavior and the textile fabric produced from it was uniform in shape and free from defects. "

Example 6

^ f ^A iTfifif ** \ 1 un ^ by U ¹¹ ^ ^- IiIy Ttem polymer

A calcium fluoride slurry with an average particle size of 0.03 m was injected into a spiral for continuous polymerization during the polymerization of hexamethylenediaomonium adipate. which contained calcium fluoride, was pressed as a diokes tape into a V & eserbad and then chipped. Oils The concentration of potassium fluoride in the chipped polymer was 0 _f 06 £ and the relative viscosity of the polymer was 46. The polymer contained O ₁

009843/1905

The nucleated polymer chips were spun at a speed of 506 m / min into a 68 Mm ₁ yarn which had a three-lobed cross-section, which corresponded to a throughput of 14.9 kg / st. In Kaaln, a very good grain line was obtained. The packages of twine wound on the spun yarn were also good.

Stretch—

The nucleated spun yarn was laid down three times and then veretreok-built, and rarely in one betrayed uncrowded titer of 3650 den on one

h bit ΒΠ

fixation ", the feet in the finished yarn had a good cross-section

Process details and the yarn properties are given in Table 3 together with those for a Yerglelchagara obtained from an unnucleated polymer and at a spinning speed of 217 m / min. "

Manufacture part Λτη / f elpee

The triple merged nucleated yarn was tufted so that a loop pile carpet was obtained.

-27-009843 / 1905

who then with a standard genius made of red, blue and yellow nylamine test dye dyed «urd ·· Sin Similar comparison yarn was made from a polymer pan Nucleating agents processed into a carpet and in colored similarly. The nucleated yarn gave a satisfactory carpet, the appearance of which was more smooth was «than that of a carpet made from the comparative yarn.

Example 7

Example 5 was repeated with the difference that the concentration of calcium fluoride (average particle size 0.03 L) was increased to 0.132 pounds and the individual items and yarn properties are given in Table 3.

Example 8 Herste? Twy? from n * ^? a polymer

Nucleated polyhexamethylene adipamide is produced in an autoclave with a capacity of 2270 liters, with a calcium chloride pulp (throughput particle size 0.03 / t) slowly being introduced into the autoclave for a period of 25 minutes at an autoclave temperature of 225 ° C and a pressure of 17.5 at. The polymer had a relative viscosity of 40 and contained 0.2j (calcium fluoride and 0.2% TiO ₂ *

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009843/1905

The nucleated polymer was spun into a yarn of 68 threads with a three-lobed cross-section on a standard pinhole weave at a spinning speed of 325-5 m / min, a throughput of 15-9 kg / st being obtained. Both the thread course of the chimney and the structure of the Otarnwiokel were good. The spinning temperature was 274 and the SpinndUsenplattentemperatur ⁰ O was within dea Bereiohe of 274-279 ° C, di "about 15 ⁰ C lower than the temperature for nukleiertee un * polymer is used.

The yarn was reinforced as in Example 5 and the processing behavior did not pose any difficulties.

Details of the procedure and the procedures involved given in table 3

Carpets

The nucleated yarn was processed sueaanen with a comparative yarn into tufted standard carpets, which were dyed with a standard dye as in Example 5. The carpet made from the nucleated yarn had a more even crimp and tuft structure and was more evenly colored than the carpet made from the matching yarn.

-29-009843 / 1905

Example 8 illustrates a particular advantage of the present invention, which is that the presence of a Ifucleating agents make it possible to use nylon-6,6 at a Spinning temperature below that satisfactory, which is normally regarded as the minimum temperature will achieve a usable product quality.

Table e 3

example 6th 7th 8th Compare Spinning speed m / min 308 308 325.5 217 CaF ₂ Oew .- ^. 0.06 0.132 0.2 - · through homogeneous particles
size of CaP ₂ (/ c) Ö; 03 0.03 0.03 ~ - average distance
of the particles of CaF ₂ (mJ 0.51 0.39 0.33 ⁰ I - ⁰ O 0.24 0 "29 0.29 0.01 DTA solidification point ⁰ C 236 235 235 223 Spinning temperature ⁰ C 290 290 274 290 relative viscosity of the
Polymers 46 46 40 45

Example 9

liu fcl ed em polymer

A series of polyhexamethylene adipamide polymers have been made that contain calcium fluoride in variable cones

-30-

009843/1905

Trations of 0.003 Me O _f 25 #, based on the polymer, contained. In all cases, these polymers were divided by injecting an appropriate amount of a calcium fluoride slurry (average particle size 0.03 / liter) into the vaporizer portion of a continuous TnT of 1 sw / liter at 4.1 kg / et at the 60 micron injection point

Spinning process

The polymer containing calcium fluoride was extruded into 10-ply yarns in each case from the spiral with a Spinngeochvindi ^ Jwlt τοη 1198 m / min. The polymer had a relative Yiekoeität of 33 m & contained 0.33 tons sueätslloh su the Caloiumfluorid.

'uh

The nylon yarns are in each case at a scattering speed τοη 1000 m / min to a ^ extended titer The draw ratios used were set in such a way that the yarns were drawn had an elongation at break of 30%. Terfahrselninsel seldom and results are shown in Table 4.

νααά. ΏαΤΛ

The nylon-6,6, which contained different amounts of CaF ₂ ,

BATH 009843/1905

- 51 -

produced 30 den games are played on the continuous · Uniform titer and on the Durazole tire rating tested as described below. The results are in the. the following table 4 together with those for a comparative sample included

Continuous titre tiBtufunff (CTE) This is determined as the largest titre deviation within each 7.6 a of a 182.9 m long test piece of the pre-drawn yarn using a continuous titre tester

Durazole Stripe Classification ( D.3.B.)

This is made by knitting a flat piece of dt « Yarn and subsequent classification according to

Standards after staining in Durazol Blue 2 Re200 Innllil The same pieces were given a grade 1, 2 or 3 in order of intensity of the visible. Stripes classified »with a rating of 3 indicating a high stripe intensity« βigtβ.

With a mean particle distance of less than 1 µ, the yarn with a CaF ₂ -GolaIt showed noticeable values in the continuous TiteTobweighing and the Durazol tire rating than the non-nucleated yarns.

009843/1905 ~ ⁵²

169U76

Example 10

Example 9 was repeated "with the difference that calcium fluoride with an average particle size of 0.1 IyLc was used at concentrations of 1 # or 2 £ in the polymer ." The numbers for this example are given in Table 4,

Calcium fluoride slurry with an average calcium fluoride _{particle size of 0 ρ} 11ι «was prepared as follows:

(a) 382 g of potassium fluoride were demineralized in 6.3 liters Dissolved in water.

(b) 527 g of calcium acetate were demineralized in 6.4 liters V / ater dissolved.

(c) Solutions (a) and (b) are boiled ο

(d) Solutions (a) and (b) are mixed quickly.

(e) The resulting suspension is boiled for 4 st and allowed to settle

(f) Ea is decanted, further demineralized water is added and the suspension is again allowed to settle and the supernatant liquid is poured off

(g) It is diluted to a 1% dispersion of CaP _{2 with demineralized water.}

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009843/1905

169U76

(h) The suspension is at the 60 # "Iu; jektionspunkt in the spiral with diner rate of 1.1 l / st I) two 2.2 l / st INJECTI, wherein an ion concentrate of 0 ^ 5 bzwo YSS> Capp * * Yarn is achieved

Example 11

Example 9 was repeated again, with the difference that calcium fluoride with an average particle size of 0.2 oy ^ at concentrations of 1 and 25 * m Polymer were used-, The Verauchosahlen for this example are given in Table 4 »

Calcium fluoride slurry with an average calcium fluoride particle size of 0.20 μ was prepared as follows:

(a) 1898 g of potassium acetate were dissolved in 8 l of demineralized water.

(b) 2412 pounds of potassium fluoride were dissolved in 3 liters of demineralized water.

(c) Both solutions were filtered.

(d) 100 liters of demineralised water were poured into "Inen. large container ^{heated to 10O 0} C and

(e) the solution of the Caloiuoaoetata was heated

at 100 ⁰ C

(f) The heated worao Kaliumfluoridlöeung at 9O ⁰ C.

«34-009843 / 1805

(g) The hot KqI ι ^ ιρ> ΉnpridlUfonin g was added to (e) for 1 min with gentle mixing »

(h) resulting suspension was heated at 100 ⁰ G 30 "and stirred.

(i) It was allowed to cool to room temperature overnight calmly.,

(j) The supernatant liquid was decanted, * and the suspension was mixed with

Water again diluted and allowed to settle again and decanted

(k) The CaF ₂ was again dispersed to produce a 2.5% suspension. In order to keep the CaF ₂ ¹ ^ suspension, it was necessary to stir _{or similar}

(1) The suspension was at a rate of 1.1 l / st or ο 2.2 l / st inserted into the spiral,

where a concentration of 1 baw «, 2 ^ CaF _{2 was obtained} ^{in the} Polsnner _o

-35-

009843/1905

Table 4

in *
polymer B & ttlo
CaPp
Deep
chen—
abstdo
in /*- DTA
B ₀ P ₀
⁰ C ⁰ I- ⁰ O Stretching
relationship
for one
30 # ige
Tear elongation Product
tivi-
indecent
ratio CoToBo D.SoB. example 0.003 1.4 222 0.7 2.8 1 * 0 6.9 3 9 (a) 0.006 1.1 223 0.12 3.4 1.19 2.0 1.7 9 (b) 0.012 0.86 227 0.21 3.6 1.27 1.6. 1.0 9 (c) 0.025 0.69 234 0.29 3.8 1.33 1.6 1.0 9 (d) 0.055 0.52 234 0.31 3.8 1.33 1.5 1.0 9 (e) 0.072 0.48 235 0.44 4.1 1.44 1.2 1.0 9 (f) 0.086 0.45 237 0.42 4 _s 0 ' 1.40 1.7 1.0 9 (g) 0.222 0.31 236 0.44 4.1 1.44 1.4 1.0 9 (H) 0.521 0.24 238 0.48 4.3 1.51 ¹ » ⁵ 1.0 9 (i) 1 0.74 233 0.23 3.30 1.16 - 10 (a) 2 0.59 234 O _t 29 3 * 41 1.19 - - 10 (l>) 1 1.4 234 0.12 3.23 1.13 - - 1i (a) 2 1.1 234 0.18 2.24 1.14 M. - 11 (U) - - 0.08 2.85 1.0 3.8 Comparison.

Example 12

In this example the CaF _{2 was} precipitated in situ using the following method «

-36 »

009843/1905

5240 g of nylon-6,6 "" salt were mixed with 2706 ml of cold water that was 1 * 67. g / l calcium hydroxide, and a solution of ammonium fluoride (BH-B) containing 4.52 g of HH ₄ F in 22 ml of demineralized water and 6 g of acetic acid was added. The resulting mixture was introduced into an autoclave with a capacity of 13.6 l and polymerized in the usual way.

The polymer was reacted with a spinning speed of 1198 m / min and spun at a Tit he are of 40 to ₀ stretched process details and yarn properties in Table 5

Table 5

CaF ₂ (#) one 0.09 Draw ratio for
30 # elongation at break 4.0 ⁰ I - ⁰ O ⁰ C 0.48 D ο T ο A ο-first stop point 239 Productivity ratio 1.40

Example 13

This example illustrates the use of a random copolymer, tius Hylon-6g6 and nylon-60

-37-

009843/1905

■ - 37 -

A mixed polymer of nylon-6,6 and nylon-6 in a weight ratio of 95: 5 with a content of 0.1 # GaF ₂ (average particle size in the pulp 0.03 U) and obtained by chip-coating the polymer, was spun and - ' Process details and yarn properties drawn in monofilaments with a linear density of 20 den at an average spinning speed of $ 305 to $ 68 ^: m / min are given in Table 6

Table 6

Spinning speed m / min 305 610 685 326 average particle
size of GaF ₂ in Ac 0.43 0.43 0.43 - Scattered relationship for one
30 # elongation at break 4.7 4.5 4.5 4.75 0-0
i ο 0.23 0.35 0.42 «Α» DTA freezing point ⁰ G 223 225 222 217
# '. ■■ -.

Examples 14-18

Nylon-6,6 with a relative viscosity of 40 and a content of 0.2 $ TiO ₂ , which was nucleated at various concentrations by means of CaF ₂ , which had an average particle size of 0.03 yK / was at a speed of 230 m / min spun into a yarn in which each thread has a titre of 150 the these conditions are

009843/1905

169U76

«38 -

for practical purposes, marginal spinning conditions for details
are given in Table 7 «,

Table 7

example Si
CaP ₉ the/
thread DTA
E.Po ⁰ I- ⁰ O 0.01 Ver «,
stretch Solidification
pinirt -iw ITaarlfi Particle
distance ■ ■ (ge
spon «=
nen) ⁰ C ■ ■ ~ 0o02 behaves
nis for
30 & Lge
Rupture exp
tion comparison nothing 150 222 0 4.68 120 14th 0.0026 150 222 +0.17 4.44 90 1.5 15th Q 0052 150 22y +0.25 4.30 80 1.2 16 όριο 150 231 +0.25 4.65 - 0.92 17th 0.050 150 234 4.66 60 0.54 - 18th 0.10 150 235 4.59 60 0.43

♦ in the chimney, cm below the spinneret plate

These results show that, under these limiting spinning conditions, a yarn with O ^ - 0 _Q > 0.2 is obtained with an axial size mean particle spacing of less than \ u ; this agrees well with the preferred conditions for nucleation under normal spinning conditions

-39-

009843/1905

Although the complete advantages of bonding are not obtained with a spacing of more than 1 U of the bonding agent, there is still a useful effect, because the solidification point in the spinning chimney is raised and thus higher spinning frequencies can be used

Example 19

BeBtiamng to whether other inorganic additives give a Wirkimg ale Kukleierungsmittel in polyamides, d _o h _o undrawn filaments with the abovementioned Röntgenstrahlenorlentierungsparaaetem result, screening tests were performed as follows:

Water-insoluble inorganic additives were dispersed at 290 ⁰ C under nitrogen in a glass tube in the polymer, the glass tube was equipped with a stainless steel stirrer spiraleiif örmigen. Water-soluble compounds were added to the polyamine salt prior to polymerization. "

The additives were determined by determining the D.TJU congealing point and by melting thin sections of the polymer in SiliconSl for 30 minutes, followed by vacuuming in SiliconöT for 15 min and cooling to room temperature classified The temperature of the melting and quenching

-40-

009843/1905

for the various polyamides used in these tests are given below «

polymer

Sohmel «- temperature

A ^ sohreokt * np * ratur

Polyhexamethylene adipamide (nylon-6,6)

Polyootamethylene adipamide (nylon-8,6)

Polydecamethylene adipamide (nylon-10.6)

Poly (J, 3 'p-phenylene-bispropyl-adipamide) (Nylon-5.Pc3.6)

300 ⁰ C

280 ⁰ C

270 ⁰ C

26O ⁰ C

245 ⁰ C

225 ° C 210 ⁰ C.

205 ⁰ C

The sections were examined under a PolymerisatioasadLkroskop, eu to the size of spherulite bestioaen ₀ Bine effective nucleation is "isplays by a marked increase, Doho 10 ° C or more of DoToAo-Brstarrungspunlct · nes *, although a smaller increase in the DT ₀ A. The solidification point in connection with maximum spherulite sizes of 20 yt, or less also show effective nucleation. The results of the readout test are given in Table 8 below

BAD ORiQSNAL —44-

009843/1905

Tabel

[Details of Additives Nucleation Tests description source annHhffTOdl * Level, at
the the to
sentence in
polymer
dispersed
became in »- ·., Te DTA-
BretarrungB—
punfct
⁰ O N ** noticeable polymer Caleium-
fluoride Caloium
acetate +
fluoride Particle
size finished.
polymer SphäroUth-
grufie 233 Nucleation
N a easy to
discovering
Nucleation Hylon-6.6 talc
(3 MgDc4SiO ₂ trading 1 - 20 finished
polymer 4th 223 Hylon-6.6 talc Usual
product 4-30 finished
polymer 20th 230 H Hylon-6.6 Comparisons commercial 0.5 - 6 15th 220 fi Hylon-6.6 sample Product,
with a
flowable
gen medium
ground 6,6 sals 60 230 HyI on-6.6 (Calcium 1 - 100 15th at the cat,
59? Ί SiO ?,
28 * MgO,
5% OaO shackle
ugue
product

Table 8

Some of the additives carried out nitrogenation tests polymer description source Level, at
the the to
sentence in
polymer
dispersed
became Spherulite
size DTA-
Freezing
Point
⁰ C N - noticeable
"" before
Nucleus
tion
N = easy
to ent
opaque
Nucleus
tion KyIcn-6.6 m1 frronlslerter
Asbestos
(a calcium
Maenesium
Silioate) baiväels— 6,6 sala 20th 229 N
ί Sfylon-6.6 Antimony-
trioxide Usual
product finished
polymer 20th 231 Nylon-6,6 Molybdenum dimil
fid trade
usual
product manufactures
polymer 20th 228 N ί
* ·· Eylea-6.6
j graphite hmndtle-
üblioh ··
product manufactured
Polyatr 15th 229 N ψ lNylon-6.6
I. Lead olefin hmadtlt-
üblioh ··
product finished
polymer 15th 223 N Nyloncm-8.6 CaP ₂ Lead acetate 4
Sodium-
woliramat finished
polymer 20th 224
I. Ä Calcium
acetate +
Kaliunfluori approximate
Hurricane
Srufie - 1 - 2 1 - 50 1 - 40 1 - 10 1 - 20
I.

polymer Table 8 (Continuation) source approximate
Particle
size Level, at
the the to
sentence in
Polymer dls ~
pergates
became Nucleation tests DTA-
Roasting
Point
⁰ C * Nylon-8,6 Details of the additions - mm TnftTinwle 206 ITylon-10.6 description Calcium »
acetate +
Potassium-
fluoride 1 - 20 finished
polymer Spherulite
big 204 N s noticeable
'"" ■ Nucleation
N m easy see below
discovering
Nucleation Nylon-10.6 Comparative sample «. - - 30th 200 Nylon 3P
3.6 CaP ₂ Caloium
acetate +
Potassium-
fluoride 1 - 20 3P.3,6-Sola 15th 190 N O
O
co
OO! Nylon 3P
3.6 Comparative sample - - - 60 179 - > -
3/1905 Nylon-6,, 6 CaP ₂ barium
chloride +
Pluokieee
acid, ml
the ener
one fld
capable V
diume ge
grind 0.5 - 6
"1-
.t
ίΐβ
.eß-
[e-
• finished
polymer 10 225 N Comparative sample 40 - Barium fluosil
cat 15th

«44 -

The above results show that numerous inorganic additives can be used to make a polymer according to the invention provided that they are used in the correct particle size (less than 0.5 /).

009843/1905

Claims (1)

May not graze changed j 45 - Patent claims I ₀ polyamide which contains an inorganic nucleating agent, characterized in that the average particle size of the nucleating agent is less than ¹ 0.5 / ^ amount- ;; and the mean maximum nucleating agent particle distance by the term 8 <2 G dt J is given in which 0 is the linear velocity of crystallization at temperature T, 3 is the mean maximum nucleation center part height distance is and XO is the distance of the solidification point from the spinneret plate is for an un-nucleated polymer when it is melt-spun into filamentso 2 ,, polyamide ne.ch claim 1, characterized ßokeimzelohneb that it contains 0.03% by weight matting agent " '}. Poiynjflid liftoh Anupruch 2, thereby gekonnzoiobnot, dtxQ oa aLo Hattiörun ^ oraitfcel TiO ₀ onholds, 0098A3 / 1905 169U76 Polyamide according to one of the preceding claims «thereby characterized in that the polyamide is polyhexamethylene adipamide or a polyamide having a linear crystalline rate of the same order of magnitude as polyhexamethylene adipamide. ο Polyamide according to Claim 4, characterized in that . the polyamide poly (oc tame ethylene adipamide), poly (decamethylene adipamide) or poly (3 » 3 'p-phenylene-bis-propyl-adipamide) is o ο Polyamide according to one of the preceding claims, characterized characterized in that the nucleating agent is potassium fluoride is ο 7. Polyamide according to one of the preceding claims, characterized characterized in that the mean maximum nucleation fraction is not greater than 1 O ₀ polyamide according to claim 7, characterized in that the mean maximum »nucleation area part distance is not greater than 0.5A (^, 9 ^ polyamide according to ainem dot · vorhargehondon standard, thereby gektmnzeLchnob that thor durchochnlttlloho Tällchiindurohm «ü8ör dea tiuklolerungefflittela smaller ala 0, Ia _x iflt, 10o polyamide according to claim H, characterized in that the normal part length duration is less than 0.05 A, iStu -47- 009843/1005 BAD ORIGINAL ^{J f} 169U76 11o polyamide according to claim 6 "characterized in that the Polyamide is polyhexamethylene adipamide, with potassium fluoride having an average particle size at a concentration of not more than 0.006 -s6 point to 12o polyamide according spoke 11, characterized in that the concentration of said Calciumchlorlde is not less than 0.06% ₀ GeWo- 13o yarn, which contains at least one undrawn polyamide thread, which is melt-spun a polyamide according to any one of the preceding claims, characterized in that said undrawn thread has a molecular orientation which an X-ray reflectance diagram gives where 0> - 0 greater than 2 isto t4 _o yarn according to claim 13, characterized in that O ^ is greater than zero ₀ 15. A method for producing a yarn according to claim 15 or 14, in which an inorganic nucleating agent is incorporated during the polymerization of the polyamide salt β, characterized in that the inorganic Nucleating agent «in» average particle size less than 0.5Al v> £ such a concentration 009843/1905 169ΛΑ76 ~ 48 - has that a mean 'maximum nucleating agent partohenabstana in the nucleated polyamide is given by the expression wherein G- the linear crystallization rate at a Temperature 2 is 3 the middle :; maximum nucleating agent particle spacing is and XG is the distance of the solidification point from the spinneret plate in the case of an un-nucleated polymer is "if the polymer is melt-spun into threads" and that "is expressed on the polyamide in molten form through at least one opening contained in a spinneret plate ₀ 16ο method according to claim 15 »characterized in that the nucleating agent is calcium fluoride and that it is in the polyamide during the polymerization of the polyamide salt in an autoclave by injecting an aqueous solution Slurry of said caloium fluoride is incorporated into the autoclave ο -49- BATH 009843/1905 17c method according to claim 16, characterized in that the aqueous slurry of potassium fluoride is injected into the autoclave for a period of 10-25 min at an autoclave temperature of 225 ⁰ C and a pressure of 17.5 atU o 18o method according to claim 15 »characterized in that the inorganic nucleating agent calcium fluoride iet, and that it is in the polyamide in the form of an 'aqueous pulp by injection into the spiral of a continuous Polymerization apparatus is incorporated »in which the polyamide sala is polymerized "and" was on one Point about 6Q # length of evaporation center * Method according to claim 15 »characterized in that the nucleating agent is in situ in the autoclave or the Spiral of a continuous polymerization apparatus a produced during the polymerization of the Polya idaalzes will, The method of claim 19 'characterized gekesrnseiehndt * that wivä Nukleierungamittel used as calcium fluoride which has been prepared by reacting dihydrofluoride HexamethylendiamiA-calcium adipate and _t istο 21, method according to claim 19 »characterized in that all nucleating agents calcium fluoride are used, -50-0098A3 / 1905 BADORIQINAL 1694A76 the conversion of aqueous solutions of calcium · ^ hyäroxyd and Aimnoniumfluorld in the presence of beelgic acid has been established o ο Process for the production of monofilaments according to one of claims 15 to 21, characterized in that "a large number of threads are pressed out" a spin finish is applied and the threads are instantly divided into several threads, each thread containing at least three threads, followed by the threads em splitters pen again be separated before winding In MonofBden " PATBNTAhWVHTB M.-ING.H.FINCKE.Din.-ING.H.tOH « Dlfl-INaS-STAEG « BAD ORiGtNAL 009843/1905