DE1669479A1 - Composite polyolefin / polyamide threads - Google Patents

Description

Kanegafuchi Boseki Kabushiki Kaisha in Tokyo / Japan

and

Snla Viscose Societa Kationale Industria Applicazioni

Viscosa Sop.A ₀ in Milan / Italy "'

Composite polyolefin / polyamide threads

The present invention relates to a composite thread consisting of two different fiber-forming
thermoplastic synthetic linear polymer components which are arranged in a side-by-side relationship and extend uniformly along the entire length of the thread and which can be crimped by treatment with heat or a swelling agent, and a method of making the same.

Thermoplastic synthetic linear polymers such as
Polyamides, polyesters, polyolefins, etc., supply synthetic ones

-2-009884 / 2009

BATH

Threads with excellent strength and elasticity as well as excellent durability and wash resistance. However, those made from these polymers have Fibers disadvantages in terms of their covering properties, their Dye affinity and its ability to attract water. the end For these reasons one is to a copolymerization, to the use of mixtures and many other chemical or physical improvements passed

Recently, among these, a method of manufacturing composite filaments has attracted interest, wherein different polymers melted separately, fed to a common opening and combined with one another during spinning are »so that a composite thread is obtained in which the various polymers are spread over the whole Extend length of a unitary thread and are connected together. The composite thread obtained possesses not only every property of the individual polymers that make up the thread, but it also has a latent crimp » which then by a simple heat treatment or its swelling agent treatment can be developed. “In the production of such an acidified thread, that is Process advantageous in which the different polymers are bonded together in a side-by-side relationship as such a procedure through a proportionate simple spinning device can be carried out * each

009884/2009

BATH ORIGINAL

but here * to achieve a good mutual "* Adhesion ßolcho polymers are used, which behaves in a way have similar chemical properties or structures. For example, a hoopolyme can be used as a component as the other component, a copolymer mainly composed of bus consists of the monomer component of the homopolymer mentioned, rervendet will. For this reason, the yarns obtained are poor in crimpability and properties cannot be improved by a combination of different fiber-forming components in such a way that the individual advantages and disadvantages are balanced against each other,

Ea has now been found that polyolefin polymers to various Polyamide polymers, which have significantly different chemical and physical properties in relation to the said polyolefin polymers have an excellent Have affinity.

It is an object of the present invention to provide a composite suture of the side-by-side type made from a polyamide polymer and to produce a polyolefin polymer which has excellent peelability without cleavage or separation of the possesses both polymers. Another task is to create a new compound thread that will match both the Properties of a polyolefin thread as well as a polyamide

009884/2009

BATH ORIGINAL

fadena owns.

The above-mentioned tasks are achieved by a process rarely producing a single-piece thread, in which vele & em swvl polymers are melted separately and pressed out on the same side through a common opening, a composite thread being obtained in which these polymers are equally separated in a side-by-side relationship Arranged over the length of a single helical thread, which is characterized in that one polymer is a polyolefin and the other polymer is a higher linear polyamide, which has repeating structural units of the following formula - {1H ( OH ₂ ) JIH.OO (OH ₂ ) _n-2 004- or

wherein m and η represent integers from 10 to 12 are used will.

Oeatl of the invention can be straight-chain * linear polyolefins Polyolefins such as s.B. the well-known Poly-ot-elefine or the derivatives of the same, should be used as an example The following are mentioned: »Polyethylene, Polypropylene, Polyethylene-1, Polypentene-1, Poly-J-methyliniten-1, Poly-4-methylpentene-i, etc. Visible to their production catfish and their molecular structure there is no limit to the polyolefins; Polymers can have both the isotactic structure and the

-5-

009884/2009

atactic structure can be used. Furthermore, the Degree of polymerisation is not important as long as the polymer is used Able to form threads.

The gemäfi the invention za used polyamines are, as is apparent from 4p above general formula, higher linear polyamides _v in which the number of Xettenkohlen- et off atoms in each calibration repeating structural unit 10 to 12, such as nylon-11, Hylon- 12, HyIon-11,10, HyIon-11, ί2, nylon-12,12, as well as the copolymers and the 'mixtures thereof. If a bylon of less than 9 carbon atoms is used in the repeating structural unit, then it occurs during stretching or in other post-stretching processing operations. Cleavage between the nylon and the polyolefin so that the desired composite thread cannot be obtained. In particular, have Hylon-6 and nylon-66 has substantially no affinity to the polyolefin, it Dafi not be used CON- (NEN process of the invention. The polyamides having the repeating structural units having more than 13 carbon atoms have lower Sohmelepunkte and are suitable for fiber-forming materials not suitable.

Higher linear polyamides, which have a carbon number in the repeating structural units in the above

009884/2009 -6-

BATH ORIGINAL.

• · _t . '

Eloquence «tipi *» · «« surrendered well · practiced. However τβη soaps to XYA ** * ldea, "whether that has been sugsnefrlssn, the warning them not wn-ngosetaten lüden diaroh Kooblnation» it polyolefins can be produced, only the higher linear polymers gate HaftungBeigenechaften mentioned over polyolefins; they can be used in the methods according to the invention.

In the case of the invention, the conjugation preservation of the two polymers according to Belleben can be selected from the range τοη ItIO up to 10: 1 (tolumen content) depending on the terwendian gas mixture; a Konjfceatiraererbaltnie doflerhalb this range results in a verainderte fjrttoselvngsfähigkeit the obtained aussjsaengeeetsten F & Jen is therefore voä berorsugterweise not Terwendet.

Oils of the two opposing polymers are separated gesehaolsen »einsela a · spinning head for geaeiaeaaes Spiders sucked »and on the same side. Throughout the same opening in an amount equal to that of the * Torbestiasrfcen Konjugationererhaitnie entapritAt, in air, or in a cold liquid HedluB squeezed out, forming a uniform thread, the connection to it is wound on a spool

Of course, any known spinning head type can be used for geaelnsaaes Spiders are used, but sur lessening τοη difficult-

009884/2009 _ ₇ _

keiten due to a large SehaelepunkiranteMoliiede swisokei ti is pre-sucked for the two polymers, sine Use spinning head type bu, as indicated in German patent application E 59 941 VIIa / 29a.

The suspended threads obtained after the process according to the invention can be pre-stretched in the usual way, and the stretched threads contain, in contrast to conventional crimped threads, prepared very strong spiral crimps . If the water is exposed to superheated steam or a suitable swelling agent, strong ripples will be obtained. The crimps developed in this way are due to the considerable difference in heat shrinkage of the polymers, namely the polyamide and the polyolefin, which have completely different properties, so that these crimps are much finer and stronger helical three-dimensional crimps than those in conventional assembled filaments , which consist of the same polymer series. Although the two polymers constituting the filament have different properties, these polymers do not split or separate even after a long use, so that when the crimp is reduced to some extent by the repeated or continuous application of tension

009884/2009

can be restored by a simple heat treatment can.

Furthermore, the one produced by the method according to the invention compound thread compared to conventional Polyamide threads are not only noticeably lighter and not only have higher strength, elasticity, and volume! - act and coverage »but it also shows an improved colorability, an improved water attractiveness etc. on. In addition, cheap olefin can be used as the one fur the fiber-forming materials are used, so that the manufacturing cost can be reduced. When in the production of conventional composite filaments a homopolymer as the one polymer and a similar copolymer when the other polymer is used, there is an increase in the interpolymerization ratio of the interpolymer for the purpose of improving the crimpability, a disadvantage cannot be avoided, namely that the threads are often sticky will. The one produced according to the method according to the invention Thread has the advantage that such stickiness phenomena and the difficulties involved do not arise at all.

The invention is illustrated in more detail by means of the following examples.

-9-009884 / 2009

ORIGINAL

For example, the non-stick strength of the two * polymers within a single thread was measured: "Pad samples with a size of about 10 cm were used. These samples were cut into a short section of the two Components separated, if they were strongly bent or treated with a swelling agent, never sB · 10 * 1 * · formic acid or the like, before the end of one separated component was drawn off at a given speed ; The "ur Tresoang * of the two components necessary tension was electrically measured using a voltmeter β you" determination was VOA using a voltage meter with a measuring range + 4 g at a Trenngeechwindlgkeit of 2.0 om / mla eesen, and the measured Zugspannungsvert was divided by the length of the connecting line of the two components on the cross section of the thread as a correction of the titer and the bonded surface and the value obtained was designated as the adhesive strength.

The percentage crimp was determined as follows: 30 threads of 25 cm in length were bundled in order to produce a sample. The sample bundle was immersed in boiling water for 10 minutes without the application of a load to develop the curls, and the sample was dried. The length of the dried bundle was _{denoted by L 1.} When the crimps were removed by attaching a load of 0.3 g / d

009884/2009 -10-

The length L _{2 was} obtained. Here, the percentage crimp was given by the following formula:

Percentage ripple * 2 ** t _ _inft

The viscosity number of nylon was determined as follows. O ₁ 2 to 0.6 g of the polymer were dissolved in Ia a-cresol at 30 ° C. so that 100 ca 'L solution was obtained. The vert of the oioh results if 1 is disregarded from the ratio of the flow conductivity of the polymer solution in seconds to the flow time of the solvent in seconds - measured with an Ostwald viscometer, was plotted as the ordinate and the consentration was plotted as the abscissa; the vert des The point of intersection with the ordinate axis when extrapolating to a concentration of 0 was taken as intrinsic viscosity

example 1

The polyolefin polymer used was polyethylene with a density of 0.930 g / cDp and a melt flow index (hereinafter abbreviated ale Kt, ASTÄ-J3-1238, g / 10 min, 190 ° ö) τοη 20 and as Polyamide polymers have been nylon-6, Hylon-11, Fylon-11,10 or Nylon 11.12 with viscosity numbers of 1.17 »1.0, 1.13 and 1.08 used. i) The polyethylene and a polyamide have been separated geechmolaen and together using a her » köramlichen spinning head 8 for joint spinning old one

00988A / 2009 - ¹¹ ~

from 50150 in etpe *

Side-by-side decay never spun, and the resulting VsAm was wound onto inor bobbins. In the PsUe rm Hylon-6 mr the spinning temperature 250 ⁰ O and in the higher polyamides * ar the spinning temperature 225 ⁰ O. The thread obtained in this way was further treated to 4.2 times its ureprün ^ liohen, voeei an eusaanengesetBter ? «Den tos 16.3 which was received.

They rereahied elgenuohied the obtained in this way nen -rerstreokten suBSHBensetsten Paden are in Table 1 susanne made

Polyamide, wel
ches with poly
ethylene verbun
which was. Hylon-6 Nylon-11, ffylon-11.10 Hylon-11.12 strength
(e / d) 3.9 4.1 3.7 3.6 Extensibility 39.4 27.6 28.5 30.6 Blastic
module (g / d) 23.3 26.5 21.8 22.9 Prosentuals
Ripple (H) 58 77 76 80 Adhesion
(g / cm) 18th 97 82 94

-12-

009884/2009

Table 1 shows that those made from higher misoh polyamides and polyethylene manufactured according to the invented process Threads considerably improved mutual adhesion properties and that, in addition, the threads treated with hot water have a high level of crimp.

Example 2

Co-spinning was carried out in the same manner and under the same conditions as described in Example 1, with the difference that polyethylene with a density of 0.960 g / cm 'and an HI of 7 (ASTM-D-1238 , g / 10 approx. 190 ⁰ C) was used. The properties of the drawn threads obtained are summarized in Table 2.

Table 2

Polyamide, wel
ches with poly
ethylene verbun
which was Nylon-6 Nylon-11 Nylon 11.10 Nylon-11.12 strength
(g / d) 4.8 5.1 5.0 4.7 Sonability ( % I 28.3 31.5 29.1 30.2 Elasticity
module (g / d) 24.1 22.8 21.9 22.0 Percentage
Crimp (%) 51 72 69 75 Adhesive strength
(g / cm) 16 89 81 87

009884/2009

-13-

ORIGINAL

The Fttdea obtained by the process according to the invention possessed excellent mutual adhesion and excellent shrinkability.

Example 3

Isotaktieofees polypropylene with a viscosity number of 1.45 and an HI of 6 (ASTM-D-I238, g / 10 <sm, 190 ⁰ C) and Hylon-66 with a viscosity number of 1.18 or nylon-11.12, with A viscosity number Ton 1.15 were separately melted and co-spun using a spinning head for co-spinning at a nozzle temperature τοη 275 ° C and a feed volume of 50:50 in a side-by-side ratio, and the resulting pad was co-spun wound with a Absug of 110 on a bobbin and then stretched to 5.0 times under dry heat and at an elevated temperature of 115 ⁰ C to form a yarn of 198 susaninengeeetzter the obtained preserved · the properties of the thus composite thread are given in Table 3.

Table 3

Polyamides with
the polypropylene
were connected Nylon 66 Nylon 11.12 Strength (g / d) 6.6 5.7 Elasticity (Jl) 22nd 28 Young's modulus (g / d) 26.9 23.2 Percentage Ripple (Jf) 57 72 Adhesion strength (g / cm) H 68

009884/2009

-H-

In Table 3 let eriohtlioh, dme the by the invention Method obtained suflaanengeeetaten 1 iden a · improved flexibility and improved mutual adhesion properties furthermore have da epeeifieche Gtewioht of the two above susaaMngeeetsten PBden geaeseen ^ and it was found 'that the most out-of-the-box pad en Made from traditional nylon-66 and polypropylene was, a specific Qowioht of 1.03 beeaS, leading to the made of Mylon-11,12 and polypropylene according to the invention set ssusairaiengesetate thread a spazifiachee G ^ vioht of

0.95, so that the last pad a proportional - had a low specific weight.

Example 4

Qeaeineauee spinning was carried out in the same manner and under the same conditions as described in Example 3, with the difference that isotactic polypropylene with a viscosity number of 1.26 and an MI of 10 (ASTM-D-1238, g / 10 cm, 190 ⁰ O) and as polyamides JSTylcn-66 with a viscosity number of 1.18 and nylon-11,12-Hischpolymer (MisohpolyBerisatlonsäurenia 90t 10) adt a viscosity number of 1.18 were used.

The properties of the drawn filaments obtained are in Table 4 compiled

-15-

009884/2009

BAU utitGlNAL table 4

Polyaaid · that bit
Polypropylene bonded
became Iylon-66 Hjrlao-11.12 Strength (g / d) 5.5 5.2 Elastic (*) 28 34 Young's modulus (g / d) 25.7 22.1 Percent ripple {%) 59 71 Adhesion strength (g / ca) 16 72

A load of 1 g / denier was applied to the above two crimped thread was applied for 10 minutes after which it was removed. After 5 minutes the above became Load reattached. After repeating this process five times, the composite thread containing Hylon-11,12 according to the invention was as good as before mutual adhesion properties »during the Hylon-66 thread containing sauté-seeded thread was largely divided into two components.

009884/2009

-16-

0 * 0

Claims (4)

Claims 1. ftueaanengeaetzter Polyolofin / polyamide jades, d "r au * a faeerbildenden Polyolsfinkoaponente and a faaerblldenden Folyamldkomponente is that Bind arranged in a side-by-since" -VerhältniB and verifiable ¹ About uniformly extend the entire length of Padene, vel- * Rather, thread develops excellent crimp when exposed to heat or a swelling agent without splitting or separation of the two components, characterized in that it contains a higher linear polyamide as a polyamide component which resembles at least one repeating structure formula - ^ HH (CH ₂ ) _m NH.CO (OH J _n-2 ⁰⁰ I- or where m and η represent integers of 10 Ms 12, btsitst. 2. Composite polyolefin / polyanide thread according to claim 1, characterized in that it is used as a fiber-forming polyyanide component liylon-11 »nylon-12, nylon-11,10, hylon-11,12, Nylon-12,12, copolymers thereof or counterfeit Polymers from it contains .. '■ -17- ^{: i} 009884/2009 BATH ORIGINAL 3 · Zuaanniengeaierter polyolefin / polyamide pads according to claim 1 or 2, characterized in that it as a fiber-forming
Polyolefin component polyethylene, polypropylene, polybutene-1, polypentene-1, poly-3-methylbutene-1, poly-4-ethylphenyl-1, sheet polymers thereof and mixed polymers thereof. 4. Composite polyolefin / polywaid thread according to one of claims 1 to 3 »characterized in that the polyolefin component and the polyamide component are present in the thread in a volume ratio of 1:10 ble 10: 1, λ 00988A / 2009