DE1469162C - Microvoids containing thread and fibers made of isotactic propylene and Ver drive for their production - Google Patents

Description

The invention relates to filaments and fibers of isotactic polypropylene or a less than 15 ° / "other olefinic or diolefinic mono- mers constructed ■ propylene copolymer or a mixture of isotactic polypropylene with less than 15 ° / ₀ of a polymer of olefinic or diolefinic monomer with a multitude of voids in the fiber.

The invention also relates to a method for producing such threads and fibers Melt spinning and drawing and, if necessary, fixing of the threads obtained.

It is well known that polypropylene threads have the lowest affinity or reactivity of all synthetic fibers to dyes or other treatment agents. Numerous attempts have been made to correct their To improve reactivity or affinity for numerous treatment agents, especially stains, however so far no really satisfactory method could be developed ^, ao

There is therefore a need for threads and fibers made of polypropylene with good dyeability and absorbency for water and for treatment agents such as those considered for polypropylene fibers such as a process for making such polypropylene fibers.

The invention provides such fibers and shows how to treat them with dyes and others Treatment agents has to proceed and how it is prevented that the dyes or other treatment agents are released again by the fibers treated with them.

Filaments and fibers of isotactic polypropylene or a less than 15 ° / o other olefinic or diolefinic monomers constructed propylene copolymer or a mixture of isotactic polypropylene with less than 15 ° / ₀ of a polymer of olefinic or diolefinic monomers having a plurality of cavities in the fiber are characterized in that these voids are of submicroscopic size and consequently have a diameter of less than 0.5 μ and the majority of less than 0.1 μ, the voids being present in the fiber in such an amount that the solvent absorbency, for 24 hours as measured by immersion in o-Dichlorbenzcl at 20 ⁰ C and after subsequent centrifugation more than 25 ° / m _0th

The process for producing such threads and fibers by melt-spinning and drawing and optionally extrusion of the threads obtained is characterized in that polypropylene or a propylene copolymer built up with less than 15% other olefinic or diolefinic monomers or a mixture of polypropylene with less than 15% is used ° / ₀ of a polymer of olefinic or diolefinic monomers used to cool the filaments formed slowly without drawing, if their specific gravity less than 0,9C0 is 20 to 160 ⁰ C ages, until it reaches a specific gravity greater than 0.900, .and then stretching at 90 to 140 ° C. to 1.5 to 7 times its original length.

The reproductions of photographs of normal fibers and threads show them typical features that are appropriately used to characterize them.

F i g. Figure 1 a is an optical photomicrograph of a filament obtained in accordance with the present invention, from the side seen and taken in dark field lighting;

F i g. Ib is similar to an optical photomicrograph F i g. 1 a, but shows a conventional, non-structured thread;

2a is an optical photomicrograph of a thread made in _{accordance with the invention with a TiO 2} filling, viewed from the side and taken in dark field illumination; .

F i g. Figure 2b is similar to an optical photomicrograph F i g. 2a, but shows a conventional, unstructured thread;

F i g. 3a is an optical photomicrograph of a hand-made cross-section (approximately .0.5 mm Thickness) of fibers according to the invention with ordinary illumination under an optical microscope recorded;

F i g. 3b is similar to an optical photomicrograph Fig. 3a, however, shows the cross section of conventional, unstructured threads.

Special embodiments of the invention consist in that the spun threads in a first, at a temperature between ICO and 160 ° C held cooling zone of at least 5 cm in length and then in a second, held between 70 and 90 ° C Kühlzor.e from 1 to 4 m in length to form a monoclinic structure cools that one. the off the spinneret exiting thread with a ratio of more than 200 withdraws that one after the slow cooling an aging at 100 to 130 ° C for 30 to 60 minutes carries out that the lower limit the size of the cavities is 0.005 μ, that the water absorption capacity is greater than 2%, that the treating agent is a dye or a polymerizable compound, a heat stabilizer, is a light stabilizer or an antistatic and that one. isotactic propylene polymer as the starting material with a molecular weight of 30 GOO to 80 CCO and a high melting point index are used. ".

It should be mentioned as a particular advantage that the drawn threads can be mixed with the steam of an organic Solvent swells or softens or soaks with the solvent and this then slowly evaporates. This post-treatment removes treatment agents or dyes deposited in the cavities particularly strongly fixed.

According to another particular process modification, the drawn polypropylene filaments in a relaxed state are subjected to exposure to a temperature of 120 to 16O ⁰ C for a period of 1 to 30 minutes.

According to the invention, structured isotactic Polypropylene filaments with innumerable submicroscopic, ultra-fine voids that sewehl in cross-section as well as in the longitudinal direction are distributed all over the thread.

These cavities are so small that they can be practically only examined with an electron microscope can be determined. However, it is very difficult to make an ultra-thin incision (less than 0.01 μ) of a polypropylene thread, and therefore even with an electron microscope only the presence of the voids was found in a sample of the structured threads according to the invention and it is difficult to accurately determine the size of the voids or their distribution state measure up. However, electron micro-

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Scopical examination found that the polypropylene threads are in a size capacity

of most cavities is below 0.1μ. . Amount of about 0.3 g for 24 hours at room temperature

The size, number, distribution, etc. of these in the- (20 ° C) immersed in 100 ml of o-dichlorobenzene and then

ultrafine threads present according to the invention for 5 minutes in the centrifuge (1370 g).

Cavities, however, can be determined in the following way 5 Then they are also balanced to their

will: . Determine weight gain. This is through

These cavities cannot be divided with the help of an optical microscope under normal lighting and expressed as a percentage of the original weight of the threads. Observe the her- (bright field illumination) according to the invention. Since the resolved structured polypropylene threads with the hollow power of the optical microscope under bright field Ίο have a solvent-absorbent illumination of about 0.3 to 0.5 μ, the speed of more than 25 ° / ₀ and in some cases even cavities in be substantially smaller than 0.5 μ, from - to 110 ° / ₀ or more. On the contrary, have hergenommen course, those who happen to arise and - tional polypropylene threads a Lösungsmitteldie in conventional polypropylene fibers sieht- absorption capacity of less than 20 ° / _0th
are cash. 15 The cavities are distributed over the entire polypropylene when the threads of thread obtained according to the invention, both in the longitudinal and in the side in the optical microscope under dark transverse direction. This distribution results from the field lighting being considered, the whole circumstance that - as already said - the inventive thread seems to be glowing, but it is difficult to make every appropriate thread glow as a whole if it can be clearly differentiated between individual cavities or to make out 20 dark field illumination with an optical microscope (Fig. la and 2a). One can look at a telescope. The individual cavities are drawn with a star nebula, which as a whole can only be illuminated with great difficulty or practically not, but in which no single star is recognized. This shows, for example, the microphotographs that can be taken. Since the resolving power of the optical graphie of la. In contrast to this, with the same microscope under dark field illumination, less microscopic observation is less than 0.1 μ is conventional, it can be said that most of the threads in the borrowed polypropylene threads do not show any such glowing threads made in accordance with the invention; on the other hand, one sees sharp and clear cavities must have a size of 0.1 μ. There are very light spots, the impermeable Verunsei noticed here that a conventional polypropylene thread with no structural cleaning or cracks in the thread will not have such cavities and that of the glow of the invention, because it shows clearly with the same microscopic threads are different.
Observation does not glow, but looks transparent A special feature of the invention, apart from sharp light spots, which are called by threads, by which they can also be clearly distinguished from contamination or cracks in the thread, is called (F i g.Ib and 2b). 35 the fact that they - if you do them by hand

Furthermore, the size of the cavities can be incised and the cuts (each with about 0.5 mm ■ directly from the molecular weight of the dyes or thickness) through an optical microscope under usual otherwise Determine treatment agents that are viewed by the licher (bright field) lighting - via the Threads according to the invention sufficiently absorb the entire cross-sectional area light yellow or dark yellow can be. It follows from this that the 4 ° according to the invention appear cloudy. In accordance with conventional poly A large number of threads produced, hollow propylene threads, which are not like those according to the invention Contain spaces larger than 0.005 μ. If threads contain voids, this phenomenon occurs

The number of cavities or the total volume does not matter. This can be seen from a comparison of the

of the cavities per unit weight of the invention Figs. 3a and 3b, in which the color is omitted

Corresponding structured threads can be seen on the basis of 45.

Absorption capacity of the threads for water and The polypropylene solvents produced according to the invention determine. threads or fibers can be passed through the

In order to determine the water absorbency, the various factors mentioned should be well defined,
the polypropylene fibers at 20 ° C 48 hours The polypropylene threads can not to a be Verin / generated drive 50 0.5 ° _o aqueous solution of a penetration, which is usually immersed for Hermittels (Liponox NCK) and porous in the position spongy or foamed centrifuge dehydrated for 5 minutes (centrifugal force synthetic resin objects are applied. So can 1370 g). Then they are balanced by using any of the weight gain for determining they cannot be produced. The water, blowing or gas evolving agents, e.g. B. a fiüchabsorptionsbarkeit is expressed by the 55 term solvent, such as xylene, or by treatment weight increase, divided by the original treatment of the threads with a swelling agent (such as chlorine weight of the threads, in percent. The benzene or tetralin according to the invention) for polypropylene .
Polypropylene fibers have a water absorption capacity of more than 2.0 ° / _{0 in} the threads according to the invention. In contrast, to be produced by that a water-soluble salt in the water absorption ability of conventional poly-60 solid form having a particle size of less than propylene filament less than 1.0 ° / _0th However, this water - about 0.5 μ diameter in melted-down polyabsorption capacity can be faulty, since propylene resin is mixed in homogeneously and the mixture is also an absorption of the penetrant then spun into threads through a spinneret, which is used to soak with the threads will ease after cooling and watering. For this reason, it is preferable to immerse it in warm water for a long time, to use the following determination of the solvent to base the absorption capacity of the ultrafine salt particles out of the threads. to solve. In this way of working, however, the

To determine the solvent absorption, threads produced low mechanical strength, and

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the process is also difficult to express technically through their specific gravity. Further

respectively. increases with increasing molecular orientation the

In the method of the invention, the birefringence index is preferably to, and also the orientation

a fiber-forming homopolymer of propylene degree of conversion, which is divided by half the width of the (HO) -

turns. Determined as examples of comonomers in the 5 refraction curve of the X-ray image

The use of copolymers be ethylene or is increasing. The degree of molecular orientation

Butene for the olefinic monomers or butadiene tation can be determined by measuring these three values

and isoprene can be determined for the diolefinic monomers.

called. As used herein the term polypropylene is the specific gravity of the threads at 30 ⁰ C

does not only mean the homopolymer and the io after 24 hours with the help of a »density gradient

defined copolymers, but also micropipes «of an isopropanol-water system,

mixtures of the homopolymer or the mixed If the threads contain a filler such as titanium oxide

polymers with less than 15% hold at least one, this must be used when determining the specific

Polymers from olefinic or diolefinic mono weight are compensated. The unstretched ones

meren. It is preferable to use an isotactic 15 threads must have a specific density as specified

Relatively small molecular weight polypropylene, greater than 0.890.

in particular with about 30,000 to 80,000, and the degree of orientation can be expressed by the double-size melt index, determined according to ASTM-D-1238- refractive index of the threads. the 57 TE. Birefringence index is determined according to the following

The polypropylene is calculated by heating according to the formula:
melted and at the lowest possible temperature

in a range that allows satisfactory spinning Γ ^ n _n -H ₁ birefringence index = -.

of the molten resin allowed by a spinning d
nozzle pressed. If desired, fillers such as

Titanium oxide, antioxidants, stabilizers, etc., such as 25 In these formulas, d is the diameter of a

they are usually used with polypropylene, in single thread, / Z ₁₁ the refractive index parallel to

the manner and amount known to the person skilled in the art, the fiber axis, n _x the refractive index perpendicular to

molten polypropylene can be added. The fiber axis and Γ the value of the delay as he

Polypropylene is generally conducted at 200 to 26O ⁰ C with a polarization microscope using

pressed through a conventional spinneret, and the threads 30 of a Berek compensator is measured. The un-

are cooled and solidified. It is very important that stretched fibers have a birefringent index

that the cooling is effected slowly, so that more than 0.010, preferably more than 0.012,

stretched threads arise which have the so-called mono-.

clinical crystal structure and a high crystallinity Alternatively or in addition, the degree of

have a degree of sation. For example, a first 35 molecular orientation of the fibers will also be as follows

Cooling zone provided, which is at least about 5 cm, can be determined:

preferably 10 to 20 cm, from the lower side of the The threads are laid one on top of the other in a row,

Spinneret extends downward. The first cooling zone until a thickness of 50 mg / cm ^{2 is} reached. Then will

is formed by a gas atmosphere that acts on the fibers perpendicular to their axial direction

suitable way, e.g. B. irradiated by infrared rays, electrical 40 X-rays, and the (H0) -Brefrungsinten-

Heating, steam or the like. On a temperature sity is measured along the Debye ring, so that

between 100 and 160 ⁰ C is heated. Below a curve can be drawn. From this curve

The first cooling zone extends from this after being measured at half width (/?), being the through

at the bottom a cylinder or chamber-shaped space, which compensates for the non-crystalline part generated scattering.

inside a second cooling zone is pens for further 45. The degree of orientation is according to

temperature adjustment. Calculated in and by this equation:

Chamber is a stream of a to a temperature 1 on - /?

inert gas heated between 70 and 90 ° C, such as degree of orientation (° / ₀ ) = ~ 100.

Nitrogen or air. The temperature control 180

the chamber described can, if necessary, cause 50 ■

by placing a suitable heating element in their interior

or cooling device is provided. The length orientation degree of more than 70%> even better

the chamber can vary by more than 80 ° / ₀ depending on the spinning conditions.

ieren, but usually a length of 1 to The undrawn threads leaving the cooling zone 4 m applied. Other suitable devices 55 will then be able to be mounted on a drum or reel used to be wrapped around a slow cool down or collected. Since the unstretched to cause the fibers or threads to produce unstretched threads, as already said, a high with a monoclinical structure. Should have a degree of orientation, they are preferred

During their passage through the controlled manner wound up at high speed (both

Cooling zone, the threads are gradually 60 for example more than 200 m per minute), and that

slowly cooled so that undrawn threads with draw ratio (ratio of speed, with

monoclinic crystal structure arise. Whichever the threads are wound up at the speed

stretched fibers should preferably have a high speed with which they leave the spinneret) is high,

Degree of crystallinity and also a strong mole- d. i.e. the deduction ratio is higher than 200, especially

Have a personal orientation. 65 special higher than 300. In any case, it is important

As the crystallization progresses, it increases so that the threads are spun and drawn,

specific gravity of the threads or fibers, and that their degree of orientation is within the above

therefore the degree of crystallinity of the filaments can be within a given range.

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As already said, the undrawn threads or naphthol dyes, disperse dyes, oils should have a specific gravity of more than 0.890. dyes, metallized dyes, vat dyes, however, most of the threads produced in this way have sulfur dyes, acid dyes, basic dyes, a specific gravity of less than 0.900. It is fabrics and stains so that they can be dyed well in depth and therefore appropriate to the threads "of a ripening or 5 moderate tint. In addition, to subject the crystal to aging treatment, the threads can be promoted by other treatment agents equation, so that the specific gravity is increased to form and sufficiently absorb, for example polymeri-0.900 or more.
The threads according to the invention are not always necessary, the ripening treatment has the important advantage that it is easy to carry out with the dyes mentioned above, even if such a treatment and other treatments are advisable in every case. agents are treated with excellent affinity

The threads can do the ripening treatment in anyone. In view of the fact "that conven-form are subjected, for example, in form 15 borrowed polypropylene threads are known for their unsanctioned Tow, wound on a bobbin or wheel, agrees with low affinity or reactivity to dye, etc. The ripening can take place under atmospheric agents and other treatment agents, it is overconditions are carried out, however, it takes place prematurely that the treated threads according to the invention in hot air or steam. find an excellent pulling power.

The temperature of aging can be within the 20's likely. This capacity is the invention range from 20 WsTiOO ⁰ C, preferably from 60 to proper polypropylene ^{threads, to the extremely low 140 0} C, vary widely; The aging time can also be attributed to the size of the cavities, which vary greatly, from a few seconds to already explained, are distributed over the entire thread. If for a few dozen hours, and if the filaments according to the invention can be treated with a treatment temperature within the range given above, this will easily be shorter. Preferably the treatment or threads will be able to penetrate. When the treatment aging has reached the cavities at a temperature of 100 to 130 ^° C., it takes 30 minutes to 1 hour there. In either case, the adsorptive power of the polypropylene itself is kept firm but necessary to carry out the aging. The cavities are so small that the resulting threads have a specific size that the adsorption force in each cavity deviates from more than 0.900, preferably from more than enough to the molecule (s) of the treatment 0.903 using the method specified above by means of firmly retaining therein. This explanation measured. is strengthened by the fact that the memory

As already said, the unstretched cold force of the fibers according to the invention for solvent threads collected on a bobbin, drum or the like is 35 higher than 1 ° / ₀ (in some cases even up to 40% or wound up before the ripening or or more). This trait is typical of those subjected to er-aging treatment. You can use threads according to the invention and in the case of the known ones, however, also - if you so wish - the shaped polypropylene threads were not found. The thread of solution, directly from the ripening or aging agent storage force, is treated as indicated in Example 1, without being measured beforehand on a 4.0.
To collect or wind up bobbin or drum. Another striking feature of the invention

The ripened or aged threads are then appropriately threads that they are more than 1%, stretched in some. The stretching can in the usual way, even more than 10%, absorb and follow water. This is how, for example, stretching is effected, hold on. It is known that polypropylene filaments are usually hydrophobic when the filaments are passed through a hot medium, such as is most commonly used in drawing in the known synthetic fibers, e.g. B. hot and their water storage power is usually under air, hot water or pressurized steam, at 0.1 ° / ₀ . This is why conventional polypropylene threads are passed through at temperatures of 90 to 140 ° C. extremely strong electrostatic, which leads to numerous difficulties in handling. B. when the threads are stretched. A larger stretching ratio, spinning, weaving, finishing, etc. In contrast, is preferred, and usually the polypropylene filaments of the present invention, the filaments of 1.5 to 7 times their original as mentioned, can hold a larger amount of water, and stretched length . The temperature at which the drawing is therefore carried out to lower the electrostatic chargeability is preferably in the lower part of the above set, so that the filaments of the present invention have the range indicated by. 55 electrostatic properties caused disadvantages

During this stretching process, the hollow will not show. The ability to hold back water spaces formed in the fibers of the invention. . is according to the method given in Example 1

The structured polypropylene threads obtained in this way were measured. . ,

have, as already stated, ultra-fine hollow As already said, have the invention

spaces that are distributed over their entire mass. In spite of the fact that the threads have ultra-fine cavities in their interior, and that is the mechanical properties of the threads, they are particularly excellent in color, comparable to those of conventional polypropylene. Examples of dyes and precursors of such threads. For example, the threads with such dyes which are suitable for dyeing the cavities according to the invention have a strength of 3 to 9 g / denier and polypropylene threads are oil dyes, such as an elongation of 20 to 100 ° / ₀ . 65 Solvent Yellow 2 (CI. 11020), Solvent Yellow 5 (CL

Since the threads or fibers according to the invention number 11380), Solvent Yellow 14 (CI. 12055), Solvent Orange 7 (CI. 12140), Solvent Red 4 (CI. 12170), Solvent Red absorb rich dyes satisfactorily, e.g. B. Azo-24 (CI. 26105), Solvent Brown 5 (CL 12020), etc .;

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Disperse dyes, such as Disperse Yellow 1 (CI. For the application of these dyes and others

11855), Disperse Yellow 3 (C.I. 11855), Disperse YeI treatment agents on the structure according to the invention

low 7 (CI. 26090), Disperse Yellow 31 (CI. 4800), tured polypropylene threads can use these dyes

Disperse Yellow 33, .Disperse Orange 5 (CI. 111C0), or treatment agents in the form of aqueous solvents

Disperse Red 1 (CI. 11110), Disperse Red 7 (CI. 5 solutions, aqueous dispersions or not non-

11150), Disperse Red 9 (CI. 60505), Disperse Violet 6 aqueous dispersions can be used. It is

(CI. 61140), Disperse Violet 12 (CI. 11120), Disperse also possible to use them in a mixture of water and

Blue 23 (CI. 61545), Disperse Black 1 (CI. 11365), to dissolve or disperse in non-aqueous medium

Disperse Black 3 (CI. 11025) etc .; Sulfur dyes, and to be used in this form. Examples of such

such as Sulfur Yellow 4 (C.I. 53160), Sulfur Blue 2 (CI. ίο non-aqueous media are lower aliphatic alcohols

53480), Sulfur Blue. 5 (CI. 53235), Sulfur Green 6 hole such as methanol, ethanol, etc .; lower aliphatic

(CI. 53530) etc. vat dyes, such as Vat Yellow 20 ketones, such as acetone, methyl ethyl ketone, cyclo-

(CI. 68420), Vat Orange 5 (CI. 73335), Vat Red 1 hexanone; lower aliphatic acid esters, such as ethyl

(CI. 73360), Vat Blue 3 (CI. 73055), etc .; Diazoformate, butyl acetate, etc .; halogenated hydrocarbons

components of azo dyes such as aniline, chlorine substances such as carbon tetrachloride, carbon trichloride,

aniline, 2-amino-5-nitroanisole, nitroaniline, toluidine, carbon perchloride, chlorobenzene, etc .; Hydrocarbon

Phenetidine, 4-benzamide-2,5-dimethoxyaniline, 4-amines, such as heptane, cyclohexane, benzene, xylene, tetra-

no-4'-methoxydiphenylamine, 4,4'-diamino-di-phenyl-lin, decalin, etc .; nitrogen-containing organic

amiη etc .; Coupling components for azo dyes, bonds such as pyridine, formamide, dimethylform

such as / ^ - naphthol, c ^ naphthylamine, 3-hydroxy-2-naph-20 amide, etc .; Ether, such as methyl ether, ethyl ether,

thanilide, 3-hydroxy-N-l-naphthyl-2-naphthamide, dioxane, etc. Also a mixture of two or more

4,4'-bisacetamides, 4,4-bisacetoaceto-o-toluidine, 3-hy- of these organic solvents can be used

droxy-N ^ -naphthyl ^ -naphthamid ^ -hydroxy ^ -naph- become.

tho-4 -chlor-o-toluidine, 2-α-acetylacetamide-6-ethoxy- albeit a solution or dispersion of a benzthiazole, 3-hydroxy-2 ', 5'-dimethoxy-2-naphthani- 25 dye or treatment agent in a non-lid, öc, a'-terephthaloyl-bis- (4-chloro-5-methyl-o-acetani- aqueous medium can be used alone, sidid) etc .; basic dyes such as Basic Yellow 2 is preferably an aqueous liquid that is mixed with (CI. 41000), Basic Orqnge 2 (CJ. 11270), Basic Red 1 0.5 to 30 percent by weight of a non-aqueous (CI. 45160), Basic Violet 3 (CI. 42555), Basic Blue 24 is mixed with the solvent, as a medium for the (CI. 52030), Basic Brown 1 (CI. 210CO) etc .; Triazines, 30 dye or the treatment agent used to the one or two hydrogen atoms on the triazine ring show a hardening of the polypropylene as far as possible, and dyes that avoid such triazines unraveling.

hold, halogenated alkylene acyl halides and coloring For the preparation of a dispersion of a dye

substances containing such acyl halides; reactive or other treatment agents can be a dispersant

Dyes, e.g. B. those with an epoxy radical; payment means are used in the usual way to the

rich optical brighteners, e.g. B. of the stilbene type, to facilitate imide formation of the dispersion and this to

azole type, thiazole type, oxazole type, imidazolone type, tri-stabilize. As a dispersant, all of these can be used

azole type, coumarin type, carbostilyl type, diphenyl type, anionic, cationic, non-

Pyrazoline type, pyridine type, etc .; numerous pigments, ionic and amphoionic surface-active

like CI. Pigment Yellow 1 (C.I. No.1168O), C.I. Pig- 40 means are used. The amount or concentration

ment Orange 5 (C.I. # 12075), CI. Pigment Red 3 tration of the dispersant can depending on the

(C.I.-No. 12120), C.LPigment Blue 1 (C.I.-No. 42595), special dye or treatment

CI. Carbon black, etc .; acidic dyes such as CI. medium, its amount, the respective non-aqueous

Acid yellow 72, C.I. Acid red 139, C.I. Acid Blue 138 Medium and its amount etc. may vary. In space-

(CL No. 62075), C.I. Acid blue 139, C.I. Acid Brown 45 common is the dispersant in a concentrate

49, C.I. Acid Green 27, CI. Acid Violet 51, etc .; concentration of about 0.01 to 3 percent by weight in the

metal-containing dyes, such as CL Acid Yellow 116, CI. Medium applied.

Orange 88, CI. Acid red 211, C.I. Acid Blue 168, CI. For the treatment of the inventive poly

Acid Brown 19, C.I. Acid Violet 68, C.I. Acid Yellow propylene fibers with a treatment liquid (a

101, C.I. Acid Orange 62, CI. Acid Red 183, CL Acid 50 Dispersion or solution of a dye or a

Blue 158A, CI. Acid Green 12, CI. Acid Violet 56 etc. treatment agent, as mentioned above) are the

Numerous other treatment agents, such as light fibers at elevated temperature, preferably at

stabilizers, heat stabilizers, surface-active more than 80 ° C, as long as in the treatment liquid

Agents, plasticizers, flame retardants, antistatic agents, immersed until the fibers are completely

Pickling agents, etc., can also be soaked in the treatment liquid. Instead, you can

inventive threads are absorbed. Examples are the treatment also after the so-called

of light stabilizers are salicylic acid esters or their padding process, after which the fibers are carried out

Derivatives, benzophenone derivatives, such as 2-hydroxy-4-do- briefly in a concentrated treatment liquid

decyloxybenzophenone, p-phenylenediamine and its submerged, expressed uniformly and at high

Derivatives, benzotriazole derivatives; organic sulfur 60 temperature (e.g. more than 120 ° C) are treated,

compounds, etc. Examples of heat stabilizers If the fibers are treated in this way, the penetrates

are various phenol derivatives known per se. Dye or treating agent into the fibers

From the aforementioned dyes and handling and is recorded in them as "real". A special

such organic compounds The advantage of such fibers is that this authenticity, especially

preferred, which a molecular weight of no more 65 special the wash fastness, nor considerably

than 500 and none such extremely hydrophilic can be improved if the fibers so treated

Groups such as sulfonic acid, carboxylic acid, sulfur are subjected to an aftertreatment, which the

contain acid, ammonium and other groups. molecular dimensions of the

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sorbed dye or the treating agent bonds, it is preferred to enlarge the cavities and / or reduce, reduce or practically completely reduce the cavities in the fibers, reduced or even substantially shrinked in order to remove the dye or the As set out below, agents are to be embedded within the fibers will. These measures are used to determine the stored 5 or.

th treatment agents or dyes even stronger To reduce the voids in the fibers, too

recorded, as they reduce or at least reduce or eliminate the cavities after the fibers, fill out better. as stated above, with dyes or treatment

In order to carry out a post-treatment to increase the size of the solvents, the treated molecular dimensions of the ίο delten fibers absorbed in the fibers are carried out with the vapor of an organic compound, the fibers can be brought into contact with a substance or solvent that treats a compound that is used to treat Reaction with the polypropylene resin is capable of swelling or softening the compound contained in the fibers, or the fibers are soaked with the said solvent so that their molecular dimensions are enlarged, and the solvent becomes. Preferably, however, the 15 is then gradually evaporated. Instead, it is also fibers beforehand with compounds that are able to degenerate with one another, the treated polypropylene fibers are able to produce a compound with a tensioned state of about 120 to 160 ⁰ C hot larger molecularate measurements, and to expose the atmosphere in the essentially free then brings the fibers in such a state that is of the above-mentioned solvent. This the named reaction takes place. So you can not only with a treatment process, for example an aromatic compound (diazo-increasing the authenticity of the treated fiber active component) with an active amino group and a sam, but also improve their transparency.
Coupling component, e.g. B. naphthol, naphthylamine examples of organics or solvents or an active methylene compound, in the above agents, which swell or soften the polypropylene resins together in the fibers as described above and which can be used to sorb and then the fibers at one temperature To reduce cavities, to reduce or to eliminate from 60 to 100 ° C 10 to 60 minutes in the presence, aliphatic hydrocarbons are treated as of acid and nitrite, so that the diazo-hexane, heptane, octane, etc., diazotized and cyclic hydrocarbons with the coupling substances such as benzene, toluene, xylene, tetralin, decalin component is coupled. The in this way 30 etc .; halogenated hydrocarbons such as tar-dyed polypropylene fibers have a detergent carbon, tetrachloroethane, chlorobenzene, etc .; class 5 authenticity (AATCC - No. 2), friction ketones such as methyl ethyl ketone, cyclopentanone, class 5 cycloality (with the hexanone friction tester, etc .; esters such as ethyl formate, butyl acetate Japan Society for Promotion of Scientific Research ge - etc .; alcohols such as ethylene glycol, cyclohexanol, etc., measure) and a lightfastness of class 4 to 5 35 which have an affinity for polypropylene,
(measured with the Fade-O-Meter in 20 hours), and When performing the solvent treatment

the dyed fibers were deeply and genuinely dyed. The solvent is evaporated by heating or in the other dyeing example, a compound is evaporated with a vacuum, and the fibers are arranged or suspended in the active amino group and a triazine with at least a steam atmosphere, so that a halogen atom together in the fibers can be removed come into contact with the steam. You sorbed and then the fibers in the presence of rods, rods, rollers, drums od. Like. Alkaline substance such as caustic soda, sodium carbonate so that they od a zigzag path for the fibers. Like. At a temperature of 40 to 100 ⁰ C to form. During the passage through the zig-zag treatment, so that the connections are zig-zagged, the fibers are exposed to a stream of the solution of a dye which is larger in its molecule within medium vapor. Another solvent of the voids of the fibers react. Treatment can also be carried out by soaking the fibers with an aromatic amine and a quinoline or with the solvent and then absorbing the phenol together in the fibers and then slowly reacting the solvents with one another at a temperature. Another example has evaporated ^{wisely below 100 ° C.}

the absorption of thioindoxyl carboxylate and an aromatic when performing this solvent treatment Nitroso compound in the fibers and lungs should be taken care of that the subsequent implementation of these two compounds fibers are not excessively swollen or plasticized together. Definitely will be within the. Excessive swelling or plasticizing Voids in the fibers connections with larger ones leads to the fact that the fibers become too after drying Molecular dimensions are formed, and their authenticity 55 tend to harden, to decrease in cross-sectional shape. or washability is considerably improved. It's flat and glued together. When the danger also possible to absorb an alkylene oxide in the fibers to such excessive swelling or plasti and then the alkylene oxide consists of ringing, it is to be countered in a suitable manner, opening to polymerize. It is also possible, for example, by reducing the affinity of the Compound containing an epoxy radical and a 60 solvent to polypropylene by adding a Compound with an active amino group to a suitable amount of another solvent (e.g. absorb together in the fibers and then use a lower aliphatic alcohol, such as methanol, within the voids in the fibers with each other ethanol, etc.), which is a relatively small amount to react. Other methods can show affinity for polypropylene. The effect of the Derive those skilled in the art from the examples above. 65 solvent can also be achieved by reducing the

In addition to or instead of the aforementioned treatment, the temperature and / or by measuring the amount to increase or increase the molecular treatment time are controlled,
dimensions of the absorbed in the fibers It goes without saying that the conditions of the solution

13 14

medium treatment can be selected experimentally speed of 650 m / min, on a bobbin,

can be arranged below the temperature control cylinder depending on the particular solder used solvent, of the particular nature of the to be loaded, wound up (draw ratio 520). The unstretched

acting fibers existing voids, etc. th, on the bobbin were wound threads

The other method for the reduction, reduction of the size 5 for 1 hour in a thermostatic chamber at 105 ⁰ C or elimination of the voids is in the stand and then in hot water at 100 ⁰ C fibers is that the fibers of an atmosphere around 3.4 times their original amount stretched, between 120 and 160 ° C essentially without a Subsequently, the stretched fibers were exposed to 30 Mi solvents, as mentioned above. Grooves heat-treated at 130 ^{0 C under tension.}

This method can, for example, be carried out io The density of the undrawn threads before the

in that the fibers were in a conventional heat treatment was 0.894 and their birefringence

treatment system treated with hot air or index 0.0121. After the ripening treatment, however with a surface at the stated temperature before stretching, the threads had a density of

is heated, be brought into contact. The time 0.904. After the final. Stretching treatment

this heat treatment can depending on the temperature 15 had the structured. Polypropylene threads a

vary, but is usually in the range of water absorbency of 17.6%, a solution

1 to 30 minutes. medium absorbency of 57.6%, a water

The methods of treatment with dyes and storage of 4.1% ^and a solvent other treatment agents, to increase storage of 6.5%.

Molecular dimensions of the treatment agent and 20 The ability of the fibers to store or retain water

for reduction ^ "withhold reduction or elimination was determined by a procedure

In the above, the cavities are in their respects a spin-dry sample, which like

Twist on fibers or threads has been explained. in determining the water absorbency

The same treatment processes can, however, be prepared as described above for 24 hours

also on the most diverse products from these 25 den in an atmosphere of 60% relative humidity

Apply fibers, for example on yarns, twisted threads, left to stand at 20 ⁰ C and then for determination

Fabrics, garments, etc. The expression fibers their weight gain in relation to their original

or threads or the like should therefore also be the weight thereof, balanced. The water storage will

include manufactured products. expressed by the increased weight divided

The microscopic percentages given in the description including the following 30 by the original weight of the fibers, in examples. The solvent storage was determined in the same way as the water storage with an optical microscope, type SKO from KK Shimadzu Seisakusho, but a centrifuged sample was used, the Kyoto, Japan, using a Huighenschen as in the above-described determination of the 10x eyepiece and an achro-35 solvent absorption.
matic objective of a 40-fold magnification When looking at the structured polypropylene and an aperture number of 0.65 carried out. The fiber from the side using an optical microscope, the resolving power of this microscope is around 0.5 μ under dark field lighting. When examined, the aforementioned 40 cavity was clearly glowing, and it was impossible to clearly distinguish each individual under dark field illumination. With the BeMicroscope with a usual condenser for the observation of hand-made cuts (each provided with 0.5 mm dark field illumination. The resolving power thickness) of the structured polypropylene threads through the microscope under dark field illumination, the optical microscope with normal illumination was about 0.1 μ. The microscopic examination was carried out over the entire cross-sectional area in the usual manner. 45 evenly cloudy yellow. The strength of the threads

. -I ₁ was 4.5 g / denier and the elongation was 60%.

B e 1 s ρ ι e 1 1 _The structured polypropylene threads were at

An isotactic polypropylene resin having a molecular 100 ⁰ C for 1 hour in a 1.5 ° / ₀ owf aqueous Disperkulargewicht of 63,000, a melt index of yaw liquid of purified CI. Disperse Red 80 4.80 and a proportion of 0.6% in the n-hectane extract 50 (bath ratio 1: 100) colored. Per gram of fiber was melted at a temperature of 240 ° C. an amount of 9.04 mg of dye was absorbed. The melted polypropylene was colored with a The fibers were deeply and realistically colored,
usual gear measuring pump to a spinneret with. . ₁ "
80 holes (each 0.8 mm in diameter) funded, ü e 1 s ρ 1 e 1 2
in order to be pressed at a temperature of 235 ° C to 55 The procedure of Example 1 for the preparation of the. Under the spinneret was a chamber of pre-structured polypropylene threads was repeated, seen that, with a length of 5 cm from the underside, the spinning temperature at the nozzle was 250 ° C. ^- the nozzle extended downwards. The chamber was surrounded by the thus generated structured polypropylene filaments an electric heating element, so that it had a water absorption of 6.2%, a water inside was heated to a temperature of 120 ⁰ C. 60 storage of 1.2%, a solvent absorption. The chamber was followed by a temperature control cylinder of 6.2%, a solvent storage of 2.8% cylinder (3.5 m length), which opens up and down a birefringence index of 0.011%. That stretched. Pre-heated air was introduced into this cylinder inspection of the threads with the optical microscope, the internal temperature of the cylinder brought a similar result as in Example 1. Keeping of at 8O ⁰ C. The compressed filaments were 65. The amount of dye absorbed by the fibers was 3.40 mg / g through the first chamber and the temperature control fiber. The fibers were deeply and genuinely colored. The cylinder passed down so that it was gradually cooled and density of the fibers before ripening or aging slowly. Then they were treated with a treatment that was 0.892.

15 16

P. ■: ι, ■ '. Hold for 1 hour. The dyed threads were

P ^{! e} washed with water and put into an aqueous solution

A mixture of 95 ° / ₀ of Example 1 Shell used with 1% sodium carbonate dipped in which they polypropylene resin and 5 ° / ₀ of an epoxy resin (product were treated for 30 minutes at 100 ° C. Then,-product of Fa were. Chemie The threads were washed with water and dried with the designation 5. The "Epikote 1009") was spun as in Example 1. Threads could be dyed deep and real,
and treated, but the spinning temperature was on. . ' .
of the nozzle 250 ⁰ C. The values of the water absorption, the beispi.ei /
Solvent absorption, water retention and the structured prepared as in Example 1, the solvent storage, and the results io polypropylene yarns were dipped before dyeing at 100 ° / ₀ of the microscopic examination of the ethyleneimine thus obtained and 1 hour at 30 ° C beFäden voted practically to those of Example 1 acts. After pressing, the threads were aligned. In the case of dyeing as in Example 1, the dye was immersed in slightly acidic water at 5 ° C. for 30 minutes and the amount of dye absorbed was 11.3 mg / g fiber. Then the threads were washed with water, the fibers were dyed even deeper and more genuinely. 15 watered and dried. The treated polypropylene. . Threads exhibited excellent antistatic properties and dyeing properties. "·

Structured polypropylene threads that are in the same :. . ■

Way as in example 1 were made, example »,

were immersed in an aqueous liquid containing 20 An isotactic polypropylene resin (the same as

with the help of a nonionic dispersant each in Example 1) was with the same spinning apparatus as

10%, based on the fiber weight, 3-hydroxy spun in Example 1, but the spinning

2-naphtho-o-toluidine and 4-amino-3-nitrotoluene dis- temperature at the spinneret 250 ⁰ C, and the up-

were pergated. The temperature of the bath was of winding speed was 650 m / min. (Draw ratio

60 increased to 12O ⁰ C, and this temperature was 25 to 520). The undrawn threads so produced had

Maintain 1 hour. Then the threads had a density of 0.8915 and a birefringence

Immersed in an aqueous solution at 70 ^{° C. for 20 minutes, index of 0.011.} Their structure was monoclinic,

which - based on the fiber weight of -12 ° / ₀ sulfuric A sample of undrawn filaments (on a bobbin

acid and 8% nitrite, wound around the diazotization) was ripened for 1 hour at 105 ° C. One

to cause a reaction. In this way, the 3p other sample of the same undrawn threads (also

Threads dyed deep red. The authenticity of the dyed (if wound on a bobbin) was 1 hour

The threads were excellent (class 4 lightfastness ^{ripened at 130 °} C. In both cases the threads had

and wash fastness as well as rub resistance of class 5). · a monoclinic crystal structure after ripening.

. . The threads ripened at 105 ° C. had a density of

B e 1 s ρ 1 e 1 5: ₃₃ 0.9032 and a birefringence index of 0.016,

The process of Example 1 for producing while the filaments ripened at 130 ° C. had a density of structured polypropylene filaments with voids of 0.9088 and a birefringence index of was repeated, but the temperature was within -0.017. These filaments were kept the temperature control cylinder to about 75 ° C of from 100 ⁰ C to 3.5 times its original half in hot water, the aging treatment was extended for 1 hour at 40 length. Then allowed to 120 ° C in a relaxed carried out, and the stretching was 30 minutes in the condition of dried air at 120 ⁰ C 4.0 times the original length. Before the ripening "set". The results of the examinations with the treatment, the threads had a density of 0.895 optical microscope, these were finished and a birefringence index of 0.015. After similar yarns as in Example 1. The through a ripening but prior to stretching, had the 45 maturation at 105 ⁰ C the finished yarns produced sublingually yarns have a density of 0.903. After the final beer, 6.48 mg of dye per gram, when the structured polypropylene threads were dyed as in the stretching example 1, and had a water absorption of 31.7%, a water absorption of 10.5%, while the through maturation storage of 8.7 ° / ₀ (measured as in Example 1), at 130 ⁰ C obtained threads per gram 10.32 mg a solvent absorption of 70.5 ° / ₀ and a 50% dye and absorbed. showed a water absorption solvent storage of 7.2 ° / ₀ (as in Example 1 of 27.4 ° / _0.

measured). Assistance

When dyeing as in Example 1, the fibers took ¹ ^

per gram of 12.4 mg of dye and were deeply colored = those produced by the method of Examples. The results of the microscopic fiber-structured polypropylene ^{threads, which were tested at 130 0} C before dyeing were the same as in the ripened, were in a bath (bath ratio E example 1, and the threads had a strength of 1:10) of warm Immersed water that was 0.01% 6.2 g / denier and an elongation of 25 ° / ₀ . . : contained a nonionic wetting agent. Then were. . Disperse Orange 1 (CI. 11080) and 48% acetic acid. Example 6. _{6o added to the bath} so that the bath had a dye-The structured polypropylene _{threads, which had been prepared according to the concentration of 2 ° / 0} and an acid concentration method for Example 3, of 1%. The threads were used for 60 minutes before dyeing in an aqueous bath (bath- this bath ^{dyed at 100 0} C. After the dyeing ratio 1:40) immersed in the 8% owf disperses, the threads were rinsed with water, evenly Blue 1 (CI. 64500) and 5 ° / ₀ owf 2,4-dichloro-6-aniline-65 expressed and dried in the air. The dyed 1,3,5-triazon with the help of an anionic wetting agent threads were then dispersed in an n-heptane containing temperature of the bath chamber was introduced. the comber was increased verauf 120 ⁰ C, and this temperature was closed, and its inside was under vacuum

set and held at 6O ⁰ C. After one hour, the threads were transferred from the chamber to a dryer at 70 ^° C., where they were slowly dried. The threads were deeply colored and had excellent fastness.

Example 10

The threads produced by the method of Example 3 were passed in a zigzag through and over rollers, which were arranged within a closed chamber, before dyeing. During their passage through the chamber, the threads were ^{exposed to a stream of steam (temperature 85 °} C.) of a 1: 1 mixture of carbon tetrachloride and ethanol. As a result of this treatment, the threads were given a higher gloss and their dyeability (absorption capacity for dyes) was reduced. Microscopic examination of the threads showed that the voids had essentially disappeared.

Ef e i s ρ i e 1 11

An isotactic polypropylene resin (the same as in Example 1) was spun with the same spinning machine as in Example 1, but the spinning temperature at the nozzle was 235 ° C and the winding speed in one experiment was 350 m / min. (Draw ratio 280) and in another experiment 80 m / min. (Draw ratio 640). In both cases, the undrawn filaments obtained had a monoclinic crystal structure. The unstretched threads wound at a speed of 350 m / min had a density of 0.8956, a birefringence index of 0.007 and a degree of orientation of 73 ° / ₀ , while the threads wound at a speed of 800 m / min had a density of 0.8938, a birefringence index of 0.016 and a degree of orientation of 92 ° / ₀ . These samples were ripened for 1 hour at 105 ^° C. and stretched 3.5 times their original length in hot water. After this treatment, the threads running at 800 m / min. Speed had been wound up, voids were created, but not in the threads, which were moving at 350 m / min. Speed had been wound.

Example 12

The threads from Example 11, wound at 800 m / min had been, as in Example 4, can be dyed in deep shades real.

Example 13

The unstretched threads obtained in Example 2 were heat-treated ^{at 100, 120 and 140 ° C. for 30 minutes without tension.} The dye absorbency (CI. Disperse Red 80), the water absorbency and the water storage ability of these fibers were as follows:

warmth
treatment
temperature
⁰ C Dye/
Fiber weight
7o water
absorption water
storage 100
120
140 9.32
6.32
1.30 19.6
10.1
3.7 5.2
3.1
0.3

The microscopic examination of the heat treated at 100 and 12O ⁰ C fibers exhibited the formation of voids, while the treated at 140 ⁰ C threads did not contain cavities.
5

Example 14

. The fibers of Example 13, which were heat treated at 120 ⁰ C were treated for 5 minutes at 145 ° C ίο, so that the cavities almost entirely disappeared.

Example 15

A polypropylene resin with a molecular weight of 143,000 and a melt index of 1.28 (determined by the method ASTM-D-1238-57 TE, but with a load of 5 kg) was spun with the same apparatus as in Example 1, but the spinning temperature was at the nozzle 280 ⁰ C, and the winding speed was 675 m / min. (Draw ratio 540). The undrawn filaments produced in this way had a density of 0.8863 and a birefringence index of 0.009. Their crystalline structure was smectic. The undrawn threads were on a

The bobbin is wound up and ^{matured at 105 °} C. for 1 hour. After ripening, the filaments were stretched to 80% of the highest possible stretch at which the fiber would break. However, there was no voiding in the fibers.

Was obtained as the same procedure is repeated, but with a spinning temperature of 27O ⁰ C, formed with cavities fibers according to the invention had an excellent dyeability.

In this case, the undrawn filaments had a density of 0.8973 and a birefringence index of 0.018. Their crystalline structure was monoclinic.

Example 16

A polypropylene polymer (the same as in Example 1) was pressed at 250 ⁰ C through a spinneret having 24 holes (j ^e 0.8 mm diameter). In contrast to Example 1, no first chamber was provided under the spinneret, but only a temperature control device attached to the bottom of the spinneret.

cylinder on. Preheated to 8O ⁰ C air was introduced into the cylinder temperature control. The spun threads were after passing this cylinder at a speed of 600 m / min. (Draw ratio 430) wound up. The un-

stretched filaments had a density of 0.8968 and a birefringence index of 0.014. The wound on a bobbin threads were matured for 1 hour at 100 ° C and the interior of which boiled down to 120 ⁰ C then in an operating with dry heat drafting cylinders,

hold was stretched to 3.5 times its original length. Then, the filaments were wound on a bobbin and heat-treated for 15 minutes at 13O ⁰ C. Cavitation occurred in the threads treated in this way. The structured threads could

with CI. Disperse Red 80 can be colored deeply. The fibers had a breaking strength of 4.5 g / denier and an elongation of 40 ° / ₀ .

Claims (5)

Patent claims: 1. Filaments and fibers made from isotactic polypropylene or one with less than 15% other olefinic or diolefinic monomers built propylene copolymer or a mixture of isotactic polypropylene with less than 15 ° / ₀ of a polymer of olefinic or diolefinic monomers having a plurality of cavities in the fiber, characterized in that said cavities are of submicron size, and hence a diameter of less than 0, 5 μ and the majority of less than 0.1 μ, the voids being present in the fiber in such an amount that the solvent absorption capacity, measured by immersion in o-dichlorobenzene at 20 ° C for 24 hours and subsequent centrifugation, is more than 25 Is ° / _0. 2. A process for the manufacture of yarns and fibers according to claim 1 by melt spinning and drawing and optionally fixing the filaments obtained, characterized in that polypropylene or with less than 15 ° / ₀ other olefinic or diolefinic monomers constructed propylene copolymer or a mixture of polypropylene with less than 15 ° / ₀ of a polymer of olefinic or diolefinic monomers used, the filaments formed cools slowly without drawing, if their specific gravity is below 0.900, it ages at 20 to 160 ° C until a specific gravity of more than 0.900 is reached, and then the stretching at 90 to 140 ° C to the 1.5 bis 7 times its original length. 3. The method according to claim 2, characterized in that the spun threads in a first, maintained at a temperature between 100 and 160 ° C cooling zone of at least 5 cm in length and then in a second, between 70 and 90 ⁰ C kept cooling zone of Cools 1 to 4 m in length with the formation of a monoclinic structure. 4. The method according to claim 2, characterized in that the emerging from the spinneret Pulls off thread with a ratio of more than 200. 5. The method according to claim 2, characterized in that after slow cooling aging at 100 to 130 ° C for 30 to 60 minutes. For this 1 sheet of photo