DE1494551A1 - Process for the production of fibrillatable structures and fibrils - Google Patents

Description

MOMrHEN'5

MOLL 3TR. 51 1 I. Nile

H9A551

M 19920/19921 Dr.K / Gi.
Case B «415

Description of the patent application of

British Nylon Spinners Ltd., Pontypool, Monmouthshire / Sngland ™

concerning:

"Process for the production of fibrillatable structures and fibrils"

The priority of filing in the UK No. 44957 of November 14, 196? will be claimed taken.

The invention relates to the production of a cohesive self-supporting structure from which fine pa-corn, so-called pibrils, can be produced. .hei can be used in the manufacture of paper and non-woven products of various kinds. The invention ^inscribed:; It also pays attention to the paper and the non-woven pro lulcte on the basis of the pibrils made from the structure, soft for the purposes of this

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Description and the subsequent claims is referred to as a flexible structure. the Invention particularly relates to manufacturing such a structure from a dispersion of a fiber-forming polymer in another polymer.

In recent years, research has been carried out in the field of the development of structures which, when filled, give rise to fine fibers which are then used in paper manufacture and in the textile industry and in related fields of application. Part of the development mentioned is directed towards the production of such structures from mixtures of thermoplastic polymers. In British patent specification 930 07 * 1, for example, a process for the production of a fibrous structure is described from which fine fibers can be obtained by an intimate mixture of a fiber-forming polyethylene or poly (ethylene oxide) and a second fiber-forming one which is insoluble in the former Polymers extrudlert and then stretching the filament yarn obtained at a temperature between 130 ⁰ C and the Extru3ionst3capcratur and then Welters treckt the yarn at a lower temperature. in this method, however, although it can be carried out so as to obtain the desired structures, a two-stage stretching of the expressed thread with limited temperature conditions is required at every stage, and the required level of

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Mood of the rate of stray with temperature can be difficult and troublesome. In addition, the two-stage stretching requires the use of equipment which allows stretching to be carried out in two stages, and this means an expense in terms of Space that is available for an existing system.

In general terms, the aim is the present Invention in the provision of a method of making fibrillatable structures from two or more thermoplastic polymers, which for a Followreiohefi work from the two-stage stretching one c-extruded continuous filament within limited temperature

not

beroiche / fehhangs. In particular, it is to sohaffen an object of this invention to provide a relatively elnfaohes, technically feasible and economically attractive process for the preparation of fibrillatable structures of two or more (thermoplastic polymers. Am further object of this invention is the Pibrillen obtained from the fibriliierbaren structures in the manufacture of paper, paper-like materials, especially for products to be thrown away after use, such as diapers and napkins, and for textile materials, such as unused toxins of all kinds.

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These and other objects of the invention are achieved along with the high procedures required to achieve the same Preamble to the following description and patent claims clearly «

Thus, the present invention provides a method for the production of fibrillatable structures from welohen Fibers can be made available " v / eiche8 because it is carried out that nan a dispersion a fiber-forming synthetic polymer as a disperse Phase in another synthetic polymer as a dispersion medium manufactures «whereby the dispersion medium 1 to 48 Oew * ~ £ in relation to the weight of the two polymers, the dispersion makes up "this dispersion is extruded and then from the extrudate the polymer" which acts as a dispersion medium served «away.

It should be noted that it is possible to do more than one

synthetic polymer in both one and both Phases, namely the disperse phase and the dispersion medium "to use" but usually only one in each phase Polymer is required, and for the sake of simplicity the following detailed discussions refer only to dispersions, which in each: 1 phase have a single polymer.

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For a more detailed understanding of the invention, reference is made to Reference is made to the accompanying drawing, which is dlsJcutlert in detail below. Owned:

Flg. 1 a Plleßblld, welohes the in a continuous Process for the production of a fibrillatable structure occurring stages explained; and

Flg. 2 a photomicrograph from a 720x magnification a fragment of a fibril, the outer one Illuminatable structure was obtained.

By the term "synthetic polymer" it is intended to designate a polymeric material that is synthesized by teohnisoh was different from a natural polymer Material or a derivative thereof

Because of the fact that the suitability of fiber-forming poly ( kidneys in the process of the invention is primarily a consequence of their physical properties and not their chemical properties), a large number of fiber-forming polymers can be used.

Among the violas, synthetic, organic, fiber-forming Polymers that can be used in this invention, solion excludes those listed under the following headings become: BAD ORIGINAL

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1. Condensation polymers in general

Polyamides

polyester

Polythioester Polysulfonamides Polycarbonates Polyureas Polyurethanes

s.B. Poly (hexame thylenadlpamld), Poly (hexamethyleneebaoamld) and poly (epellonoaprolaotarn)

like s.B. Poly (ethylene terephthalate).

2. Condensation polymers are well-developed elastomers » character

Polyester urethanes

^ is implemented

N-subdivided Polyamides

such as eolohe, where a Qemlsoh of a hydroxyl group-removed meoh polyester «It is an aliphatic or oyoloallphatlBohen Dileooyanatfi which not used in molar excess and also not in a molar excess during the entire reaction period may be present *

like a.B. H-Alkylpolyemlde, e.g. those, where a Laotian «with a N-aubstulated aminosllure is implemented.

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3. Addition polymers

Polyhydrocarbons

Polyether

Polystyrene

Polyacrylic and polymethaoryl esters Polyvinyl chloride polyvinyl acetate

like 2.B. Poly (ethylene), poly (ohlortrlfluoroethylene), Poly (tetrafluoroethylene) and Poly (propylene)

like s.B. Poly (ethylene oxide) and Poly (ethylene oxide)

like 2.B. Poly (methyl methacrylate)

Mixed polymers of the polymers listed above can also be used"

The al · Dlsperetonsmedlum uses · polymer, ie the
Medium in which the fiber-forming polymer is dispersed
Phase dlsperglert, must be at least globally inert towards the feserblidenden Polynians, since if the two react to one another to an essential extent, a homogeneous and not a heterogeneous system would be the result. In addition, the two polymers must not lie in a row; 1 be tan. A reaction causes the polymer
which forms the Disperelonsmedlum, and those of the dl -

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person phase can, however, be very difficult in cut rusting ends. take place to a smaller extent.

Because the imaginable structure is made of the faaerblldenden Polyraer is obtained, the polymer * which is the dispersion - medium, based on its suitability for the particular iaoerbildendo polymer and, but to a lesser extent ^ the Properties that it has itself can be selected. For each fiber-forming polymer there is generally one Polymer «which is extremely satisfactory as a dispersion medium for this. Each for a given fiber-forming polymer selected as the dispersion medium Polymer is based on its physical properties, its melting point and boiling point, its lightness who mixes it to make a dispersion, economic factors such as availability and costs and the like. The ease with which the polymer is removed from the

other extrud at can be removed, let often a / Pak tor of It is necessary because it determines the suitability of the polymer as a dispersion · « mcdium determined. For this reason, it is sometimes appropriate to use a polymer as the dispersion medium, which is composed of the extrudate through the selective dissolving effect of a common one Solvent can be removed. Or which has a lower melting point than the fiber-forming Having polymer.

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If the fiber-forming polymer present in the system is ο in polyamide. such as poly (hexamethylene adiparaidK poly- (hexamethylene sebaoamldH ^^ (epailonoaprolactarn) »copolymers or copolymers of other polyamides or a like ζ.B. polyethylene terephthalate
Polyester / isfc, then is a very suitable polymer for that

Use as a dispersion medium a polyether such as a

additional poly (ethylene glycol). Polyglylcole also have the / advantage that they are readily soluble in common solvents such as water, "as methanol, ethanol, acetone, Dlchloräthyl & ther, Äthylaoetat and toluene, all of which preferably hot (about 50 ⁰ C) to be used.

are

From the economic point of view / the relative cheapness of the polyethers and their accessibility further recommendations for use as a dispersion medium. A useful poly (ethylene glycol) is one which is a Molecular weight in the range of 10,000-20,000, such as a poly (ethylene glycol) found in the ribbon under the Name "Carbowax 2OM" is available. Am lower glycol Molecular weight can also be used as a dispersion medium, but it generally provides a DI-

Considering the persion of the polyamide or polyester / as light as that Higher molecular weight glycol. So it is to attainment a * dispersion of a polyamide or polyester using a low molecular weight glycol as Di3per3icnsnedium often necessary a dispersant to be used, such as stearic acid, zinc palmitate or poly-

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amides, which contain blocks of polyethylene glycol.

The expression "dispersion", which is used in the description and the claims, is intended to describe the physical state of the system which is obtained by mixing the two polymers and which, upon further processing according to the invention, produces the desired fibrillatable structures. In short, the two polymers form a dispersion when they are mixed together to such an extent that a suspension of particles of the fiber-forming polymer as the disperse phase in the other polymer as the dispersion medium is obtained. The extent of the misalignment of the two polymers, a term that is briefly outlined by the expression "degree of misalignment ¹¹ ," thus plays an important role in the process according to the invention and, generally speaking, it can be stated that the feasibility of the process depends on the degree of mixing, which is so high that a dispersion of the fiber-forming polymer in the other polymer must be obtained and this can be empirically illustrated by considering the two products.

obtained when the two polymers are mixed too much, if there is a tendency for the formation of a homogeneous system, or if they are insufficiently mixed, a condition which can be maintained by the presence of aggregates from the fiber-forming polymer

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featured is facing the product from a dispersion of one polymer in the other bsstoht. Under the local conditions shows the resulting The product has little or no tendency to fibrillate »especially in the absence of additional process steps, χ * ie e.g. hot and / or cold streoken, and is worthwhile through a surplus of films present in proportion to fibrils. The product obtained by processing a dispersion according to the invention is, on the other hand, is predominantly fibrillar in character and, as a result, can very easily become f!

An exhaustive Besehreibung of Misohungsgrades, which corresponds to the optimal operation of the erflndungsgemäßen process is however obviously not feasible, but it is known a number of factors that are important in this regard and which (for a particular system determine the degree of mixing and / or required degree of misalignment can be assigned.

First and foremost is the quantitative ratio of the dispersion medium to the disperse phase · in the system an important factor for the successful operation of the process. In this connection it was found that

the polymer forming the dispersion medium is no more than •: 8 Gsw. "# In foezus on the weight of the two polymers

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should matter to the system. The presence of this polymer in amounts "in excess of this number" has a detrimental effect on the effectiveness of the process, an influence which becomes more important with increasing amounts of polymer inside. The effect of the incorporation of a larger amount of the dispersant in the system on the feasibility 1st wahrsctjelnllhh the inclination zuzueohrelben which then place the two W polymers of the day, to give a different Mlschungssysten as a dispersion comprising processing in accordance with the invention, a fibrillatable structure yields _o In any case, practice has shown that operation of the process with amounts of polymer which act as Disperslonsmedlum-soll s above 48 OEW .- # a structure results, which has no appreciable flbrillaren character. Indeed contains

produced even in the most favorable case a so / structure / a considerable proportion of film and can only be brilliantly shined with difficulty, and there are then additional Process steps such as hot and / or cold stretching of the extruded material are necessary. The preferred range of composition for use in the process of the invention is 10 to 40 wt% of the polymer which is the dispersant forms, and 90 to 60 ow.-Jg of the fiber-forming polymer.

The duration of the season, the temperature in the cases « in which the polymers are mixed in the molten state, and the manner in which the mixing is carried out,

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for example the Mleoh speed, are all factors which for a particular system is the current degree of dissolution determine. The influence of these factors on the degree of misappropriation and thus their influence on success, in other words, on the method according to the invention is when applied on the poly (hexaethylene adipamld) / poly (ep3iloncaprolaotaiu) -HiBohpolymer «/ poly (ethylene glycol system Explained in example 6.

Βοία Mixing the two polymers but making the dispersion prior to pressing are generally conventional Methods and devices applicable. At a

Appropriate method »Especially when the particle size the polymer is not similar, the two polymers are melted together or separately, and then mixed in the molten state. This method lends itself very well to being applied on a continuous basis Procedure * for the division of the f ibr & lable structures » The niche is done in a pump prior to extrusion «Zn can be done in a batch process the molten polymers are mixed, forming a dispersion «and swar in an autoclave with is equipped with a stirrer.

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It can also dry Mieohverfahren, for example those using a ribbon mixer # applied the two polymers will be available in powder and chip form.

The term "extruding or pressing * ¹ is in this description and in the following in a PatenanaprUchen

ψ sense used that this includes all means

nindimlt which the dispersion is made to flow can. The respective extrusion location that is in each individual Case used depends on the mixing process and also on the form in which the fillable structure is desired. In the following description, which one Contains series of processes for the production of the fibrillatable ι structure by extrusion, it is always assumed that the dispersion is made by solubilizing the two polymers

k has been established.

In one embodiment of the invention, the filler has bnre structure takes the form of a ribbon and is obtained by Extrude <* ar Dispersion Through An Orifice In A Car

telaven on a flat Pl & ohe, like z, Sj. a casting wheel, and then Bntfornen, boiepielswalBe by Wasohea des DIa-

. perslonsmediums. '- ·

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In another embodiment of the invention, the fibrillatable structure takes the form of a web and is preserved by spraying, for example from a spray gun, of the dispersion on a receiving surface, which is stationary can be or can move, and then removing, belapl'iswelse by washing, the dispersion medium. The receptacle can be solid or perforated, i.e. it can consist of a * plate, a Sohlru, a conveyor belt or consist of similar ones. It can be continuous or move gradually, old or without back and forth- I walking and / or circling movement. The admission area can for example consist of a pair of rotating rollers ode *. * it can be designed in such a way that a pre-formed Open stand made from predetermined Oeetalt will.

In another embodiment of the invention, the f1-brilliant Structure can easily be manufactured in a single continuous process in which a dispersion is carried out an opening «is xtruded, whereupon the Extrudet In Form of continuous strands is passed through a zone, which * contains a solution oil for the dlapersionsnedlun, wöbe-, the dispersion medium is removed from the 8trangs and fibrinable structures are obtained, which then for example be collected on a winder grains.

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The polymer of the dispersion medium can be derived from the extrudate "ground away" in various ways. Am very useful Method and one that has been prepared solvent extraction using a suitable solvent. The detergent used in each case depends on the nature of the polymer which is used as the dispersion medium, and it must be used for this polymer be an eelektlvea solvent. Water is often a particularly useful solvent. Vena s.B. el · Dlsperslonsmedlum a poly (ethylene glycol) for, for example, a polyamide or a polyester is used, then Olykol Anaohllefiend duroh Löaungamlttelextraktlon with water ata Solvent must also be removed from the extrudate. FtIr a the removal of the ala diaper becomes economic art lonaetd ium used polymers old advantage in an icon * · ' tinulerilohen Wolae carried out, whereby the extrudate beieplela « wise Moving a zone in the form of continuous strands will »which a selective solvent for this Contains polymer.

Other means which are suitable from the extrudate Remove the polymer used as a dispersion medium s.B. chemical or physical decomposition. If the material used as a dispersion medium is used as a matter of course Melting point which is lower than the boiling point of the fiber-forming polymer, then the extrudate

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aui one above the sonic point of the dispersion medium but the temperature lying below the softening point of said polymer is heated and the liquid obtained be separated for example by filtration.

It should be noted that the treatment of the extrudate In the catfish just described, it is practical for removal

of the entire polymer of the dispersion medium leads to " but generally does not result in complete removal

That after the removal of what was used as a dispersion medium Polymer obtained from the extruded product is a cohesive, three-dimensional »self-supporting» fibrillatable Structure. The fibrillatable structure can be examined under the microscope Scales take a number of forms, but broadly speaking, 2 major classes can be recognized. At a this! (let the individual fibrils form the structure «· j stones of the structure, being the cohesive and self-supporting The nature of this is due to the frictional effect between the individual fibrils. With the other class the structure is composed of a mass of fibers » which are arranged in strands which have larger longitudinal dimensions than those which have the fibrils, into which the strands disintegrate when tension is applied to them. The structures differ focussing on your ability to fibrillate

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len without the need to apply a certain level of stretching to the structures. By the term "certain degree of scattering" it is meant that sealing glasses can be obtained from the perceptible structures without the application of a process to the same in which the structure would be caused to expand by more than 25% of its length. That is, f that expansion of flbrllllerbaren structure in such small amounts, such as 5 - 10 Ji resolution thereof results in fibrils.

What shape these imaginable structures of this invention also always assume that you do not adhere to just f ull-clear things Material but also film. This is called a condensed, moderately fibrillatable structure. On the other hand, duroh can be suitable Descent of the process a structure can be obtained, welohe: .in a high maggot can be felt, i.e. that it sieves almost entirely of cases or fibers with little or do not put a film in between. ,

The inflatable structures can take the form of a ribbon, Giner foil, made of strands, threads, webs, cotton swabs or the like possess ^ and they can be found, for example, as insulation packaging or packaging materials or during filtration. Use. The tangible structures in the form of strands

genes or pads can be easily twisted together.

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If austerity or threads result in a rope-free structure. The rope structures are good for filter covers in the Flltratloneteohnik, such as ζ · Β · as egg arette fillers.

The fibrillatable structures provide glasses when dissolved. Suitable processes for dissolving the fibrillatable structure are mechanical processes, such as bending, hitting, rubbing, dewarping or guiding the structure around under tension, including a sharp edge. For the threshing device available for the treatment of the fibril harsher structure) ^ ^ett f ^β * ° fiRj eo it is necessary to report this in StUoke. The shapeable structure can be cut into suitable staple lengths, that is, in lengths of 19 - A3 * an, preferably 6.3 ~ 50.8 n, and was made by hand or on various conventional devices. For continuous processes Ie Groften scale cutting in allgenelnen 1st unnecessary, which abhüngt from the sun Dreeohen i AuerOetung used. To support the dissolution by dewatering, the fillable structure, if necessary, has been cut into soldering lines suitable for handling. Dispersed in a liquid Nedluai.

The structure that can be dazzled can also be subjected to submission

under

the struktui / elne Intensive continuous Vltraeohallbratlon be dissolved, for example a Flbration

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with a frequent: of 10 Klloherts, welohe belsplelsweise is sucked in by magnetostriction.

The fibrils duroh resolution will receive the erflndungsgeetteen flbrlillerbaren structures * have a Vlelsahl of forms, but when the fibrils ψ beslteen predominance in general rod and lomellenähnllohe body a dimension much welohe grttler than the other

both dimensions Ut. Part of a typical case 1st with very high magnification in microphotography from Flg. a selgt. I wet the fibrils, if they are bwt with the fingers of the hand, what a fibrous OrIff. Am characteristic of the Fibrils are their highly irregular surface Ie The microscope adhesive tab, which gives you its high level of specificity Surface is as it is indicated by Poroaltlltiteaeungen will. Typical fibrils according to the invention, old spesl Fish surfaces in the order of 800 to 600 o «/ g. The high absorption capacity of the fibrils for water

clears the ease. old which it is in the same. and also in other liquids can be puttied, and the water-moist leaves thus obtained are considerable Wetting force due to twisting and twisting of the individual fibers. So are the fibrils for *. the manufacture of a number of objects using wet deposition processes especially useful »because the fibrils

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bind when settling from a liquid suspension " for example on a screen "together" with a cohesive one Structure is obtained · In this context, similar products can be made from the fibrils using paper making equipment These table-like products can be made entirely from bulbs or they can be formed from a mixture of fibrils and staple fibers. If such Panels are exposed to heat and pressure after drying » so the fibrils can weld together "so that a solid and uniform panel is obtained. On this catfish can Papler-like products are obtained «which are completely made of synthetic polymeric material and which have considerable strength without useful binder material must be added.

The following graph is for the purpose of a better understanding of the method according to the invention when applied to the manufacture of wet-laid products specified «

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Flexible structure

cut in staple fiber!

Staple fibers

Soles for making plugs

Slurry of staple fibers

mixer

Suspension of pellets in

waaserfeuohtes leaf,
stored on a screen

water-moist leaf, deposited on an umbrella

Nafi press KfaBpresae

Calender to melt the bowls

calender

Product role

The sealing goggles are particularly suitable as a binder to hold other large materials together, such as fiber webs, those involved in the manufacture of non-woven items

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uses «earth o
of all kinds / The kind of non-woven objects obtained

and the qualities which they display

can in many ways ¹ * ⁰¹¹ ** ¹⁰¹ * ¹ ^! to be modified

When used as a binder for fibrous webs

the pebbles are soled with the fibers of the web and then activated, that is, by means of a suitable treatment on a belsplel basis made sticky by heat or a solvent.

As already mentioned, is 71g. 1 a Pließblld, which a suitable trlrtsohaft high system eur manufacture one flbrilllerberen structure explained, the faeerblidende Polymer in the ohmic state at a sat speed and a constant volume of one poly-oil supply A led through a Meflpuoipe in a Mlsohpunpe becomes «before« an entry into dl · Nleohpuape mixes the fiber-forming polymer old molten polymer, which the Dleporslonem «diuoi represents and you raw a Neepump of Polymer reserve B is supplied. The two watching Polynerotröme for the production of a dispersion is described in executed by the mixing pump. The Misohpuiape is constructed in such a way that mixing in a counter? high speed, more intense Turbulence and low stay volume βloher carried out will. A very effective pump for this purpose is one Duplex-Heßpunpe, which a stay volume of 1.1 / 2 oom owns. In connection with the mixing in the pump, the

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The resulting dispersion is squeezed out through an opening in the form of an endless thread and then passed through a solution bath, in which the solvent is the potentiator Debt selectively removed. The inflatable thus obtained Structure is dried and then put on a product • guided take-up reel

Definitions of AosdrUoke used in the following examples

The Ausdruok "relative viscosity * means the ratio of absolute viscosity at 25 ⁰ C (in Centlpolse) a solution of the faserblldenden polymer in 90 pilgrim formic acid (10 # of water and 90% formic acid) to the absolute viscosity at 25 ⁰ C (in Centlpolse) of 90 lgen formic acid.

The elongation properties of the fibrillated structures were measured on an Instromneßgerät using 2 cm experimental: Mngo and <Inor extension of 100 % per minute (2 cru / rain

Äeinöesen Ki'Guztcopf-C.-esch SPEEDYR The measurements were carried out at R ^c v.T '";c;!R.p3rni; ur and 67 $> relative Fsuciht".

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The tenacity of the inflatable structure was determined from the Elongation strength calculated and expressed in g / benle drtbkt. These values can be converted into values « which are expressed in lb / in / oz / yd «by adding 17 multiplied.

The freedom of the pibrils was determined by "T appi test T 227m 50? The details obtained from this test are expressed in the usual Canadian standard freedom numbers, which represent the number of ml of water which come from an aqueous suspension of the pibrils under certain conditions Conditions drain.

In the examples, all parts are expressed by weight and the compositions are given in parts by weight or by weight « if nothing else is noticed 1st. '

The following examples are given to illustrate the invention. They are not to be understood in a restrictive sense «

The name Carbowax "appearing in a number of examples" is a registered trademark.

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example 1

2G g of a mixed polymer of 80 parts of poly (hexamethylene adiparnide) and 20 parts of PolyCepsilon-caprolactaa) and S g of one Poly (ethylene glycol) with a molecular weight of 1S000 to 20,000 which is commercially available as the Carbowax20M together in a glass vessel under a nitrogen atmosphere warmed up. The heating time was about 30 minutes and gradually

W course of this time, the temperature inside the Geflsses risen to about 27O ° C, Bs has been observed that after the lapse of 30 minutes, the polyamide copolymer and the poly (ethylene glycol) -Dispersionsmedium had not mixed in substantial "Ausmaft" The dispersion of the The mixed polymer in the polyethylene glycol was obtained by stirring the mixture for 3 minutes with a helical steel stirrer inserted in the glass jar and operating at a rate of 10 revolutions per minute. Dms vessel

\. was then removed from the heater and a portion of the molten dispersion was drawn off by raising the stirrer above the melt plane in the vessel. The polymer mixture suspended from the stirrer solidified on cooling to give a tape. The tape thus pulled out of the liquid was then removed from the stirrer and the poly (ethylene glycol) dispersion medium adhering to it was removed by washing the tape in water. A fibrillatable tape was thus obtained, which consisted of a plurality of fibrils of the polyamide mixed polymer, the single ones

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Pibrils were held in place by friction. Oils pibrils were aligned parallel or substantially parallel to the longitudinal axis of the belt,

The Fibri liierbare band had a relative viscosity of 4I ₉ O. This was a 8.4 Iige solution of Polyhexanethylenadlpanid "tr Bostlaaung used" the term formic In 90 vol lfcosBMB lös borrowed was.

A cheap analysis of the fibrillatable tape showed that this contains 32.4 asine end groups and 72.0 carboxyl end groups * held »expressed as gram equivalents per million gram des Band.

Example 2

80 parts of polyethylene terephthalate) was added 3 ^1/2 hours in a "nit a stirring device equipped Aitoklaven to 283 ° C is heated with the agitator 12 executed Un 1 flu f ο per Hinute.

Alternately, a vacuum and a long "saner stream of nitrogen was applied to the autoclave to un vorhindern that the polyester _v entpoiymerisiert

ZO Veite eirss Hily (ethylcnglycol) with a molecular weight. 15 000 b: 'is 20 000, which is sold under the name Cnrhovax 20fi ill ti i i: -1 _y ' were i: ugeset;: tu?; Dd? .C mixed

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treatment was continued for 30 minutes. 0er RQhNr 'performed \ Z revolutions per minute and after the course of the SO meowing the polyester was diapergated in the polyethylene glycol dispersion medium.

The product was made on a stainless steel
Casting wheel poured out and formed a band. The tape was approached F through a water tank of a winder.

The band thus formed was then «1t helsse ·. Washed wet, we remove the poly (ethylene glycol) component au and that
The resulting fillable product was in the pore of a tape, which consisted of a variety of polyester fillings,
which were aligned parallel or essentially parallel to the band axis. The polyester eyeglasses were held in the band shape by the internal friction between the individual pibrils.

Above the pibrils, the fibrillatable tape still contained something Film that connected the individual pibrils.

When the fibrillatable band is bent over a small radius odor exercise under tension? a sharp edge was drawn so it disintegrated into the individual fibrils.

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A mixture of 1280 parts of poly (hexanethylene adipair Id), 320 Parts of caprolactan, 1000 parts of hater and 9.4 parts of 20 liters

Acetic acid as a stabilizer was placed in an autoclave in a

2 heated inert atmosphere until the vapor pressure had risen to 17.6 kg / cm and the mixture was stirred with an anchor-shaped stirrer that carried out 12 revolutions per minute. Oer pressure in de * autoclave was kept for one hour at the specified value and then decreased over one hour to atmospheric \ pressure and during this time the temperature ^rose! the mixture to 260 ° C. After the mixture was kept at atmospheric pressure for 10 minutes, 350 parts of poly (ethylene glycol) having a molecular weight of 150 to 20,000 were added over 10 minutes and the mixture was further stirred and then at 265 ° C. for an additional 5 minutes held. After this time, the polyamide copolymer was dispersed in the poly (ethyl glycol) dispersion medium. The melt was then poured onto a stainless steel casting wheel and it was in the form of a strip

Product was passed through a winder water bath

I ( fed · ·

The strip was then agitated in hot water see u to remove "the poly (ethylene glycol)" dispersion medium and finally dried. The plugs were in that fibrillatable strips parallel or substantially parallel

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aligned to each other and to the longitudinal axis of the strip »vie could be determined by microscopic examination of the product. ,

j The fibrillatable strip contained not only fibrils, but also film · This film »of the individual fibrils from each other separates and connects, could also throw in the microscope established.

• The mean strength of the fibrillatable strip, as calculated from the breaking load values, was 7.55 χ 10 " ² g / denier in the longitudinal direction and 0.963 χ 10" ² g / denier in the transverse direction.

values were 14.9 and 7.7 expressed as a percentage.

The fibrillatable strip was then crushed in a non-rotating blade grinder was ground, with a large number of bulbs • Was obtained: • The fibrous sludge was filled with water Canadian freeness by 720

10 g of a mixture of 3 parts of staple fibers made of poly (hexa-methyleaadipa «id) of 6.5 naL and a rush fiber denier of 3 and 1 part of those produced in the above catfish

. ten fibrils were mixed in 3 liters of water, with a « Wetting agent from Dispersol VL was added «This mixture was

, then on a sieve with a mesh size of 0.152 mm and one

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Poured in a diameter of 23.5 cm, which is in a hand-held cupboard found · After all the water has been removed the sheet obtained was removed from the sieve by a filing technique.

The sheet thus obtained was heated for 1/2 minute between aluminum plates, the surfaces of which were provided with a Teflon coating, at JJO ⁰ C under a pressure of 28 kg / cm ^2. As a result of this heat and pressure treatment, the pibrils melted and there was a coherent sheet which had the appearance of leather. V ■ '■■■■■

The procedure described for the preparation of the sheet was repeated using 10 g of a mixture from 3 parts of the poly (hoxaaethylene adipamide) pibrils as they are were obtained according to Example 1 and 1 part of the mixed polymer fibrils, as obtained by the method described above · The sheet was made under the same conditions as given above, hot pressed to give a very tough paper product.

Instead of the pibrils with staple fibers or pibrils from one To mix other polymer, they can also be used alone for production of a sheet-like product can be used. Due to their particular properties, the pibrils disperse easily, unstable dispersions to give, which in the usual r-apievhern; . ^ longitudinal process without the addition of the surface

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influencing agents can be used. These fibrils can therefore be used in the usual papermaking machines.

The fibrils can thus be added to the beating device and passed through the refining device into the head box in order to then reach the sieve of a Fourdrinier machine. From there, the Journal of the wet press can be fed and then kenvmlzon over Trok- ψ, calenders are out Uta be finally wound up as Barin.

In the manufacture of such sheet-like products, the fibrils can be made with natural or synthetic staple fibers and / or cellulose pulp are mixed.

Example, 4

A mixture of 1380 parts of caprolactan, 1000 parts of water and 9.2 parts of 20% acetic acid as stabilizer was heated and stirred in an autoclave under an inert atmosphere until the steam pressure had risen to 17.6 kg / cia ² . The anchor-shaped stirrer was rotated at T2 revolutions per minute. The pressure was one hour tang to 17.6 KSS / _v cer kept the temperature of the car Ulsveninhalts au * 255 ° C increased by discharging steam. The mass was then kept under atmospheric pressure for 30 minutes and 600 parts of poly (ethylene glycol) with a molecular weight of between 50000 and 20000 were made

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added and the mixture was kept ^{at a temperature of 265 ° C. for a further 15 minutes.} After this time, the polyamide was dispersed in the glycol. »The peel was then removed from the roaktitnsgofäß, poured out in the form of a tape, washed where it and gawashed, Uta removed the polythylonglycol dispersion medium and finally dried to create a fibril * To yield lbarless end, which consisted of a multiplicity of fibrils, which were aligned parallel or substantially parallel to the ligament axis, with the like between the fibrils

little film was available.

2.5 g of the poly (epsilon-caprolactam) fibrils were 7.5 g 6 mm long staple fibers made of PolyChexaraethylene adipamide? with a fiber denier 3 mixed in 3 l of water containing a few drops of Oispersol VI * as a wetting agent. In the one described in Example 2 Way was then created oin sheet, the ity2 Minutes lan ;; hot-pressed at 22O ° C under a pressure of 28 kg / cm whereby the fibrils were activated, i.e. melted, so that the staple fibers were glued together. A textile-like material was obtained in this way, which is a leather-like substance ti.ges appearance and was surface-stable and a good one Exhibited tensile strength.

peispiaj, 5

This example explains the effect of different temperatures fvi ' the melt, the change in the fUUu speed and

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PolyCäthylenglykoD treatment on the nature of the resulting fibrillatable structure.

nine mixture of 1280 parts poly (hexaraothyleneadipanide), Parts of caprolactam, 1000 parts of water and 9.4 parts of 20 tiger uäßrigor acetic acid was placed in an autoclave under an inert atmosphere heated and stirred until a vapor pressure ton 17 “6 kg / cn was obtained, the pressure was reduced to this value held for 1 hour and then reduced to atmospheric pressure within a further hour while steam was released

The temperature at which the Scheelze was kept was de * speaking of the table listed below changed »After 30 minutes at atmospheric pressure, 3S0 parts of poly (ethylene glycol) »It has a molecular weight of IS 000 to 20,000 added in the course of 4 minutes and the mixture with stirred with an angled stirrer for different periods of time, the stirrer running at different speeds, which can also be found in the following table. Oils Melt was then poured onto a stainless steel casting wheel and the tape obtained was passed through water and fed to a take-up device.

The tape was then washed with hot water from 70 to 100 ° C, ure to remove the poly (ethylene glycol) dispersion medium and finally dried, u * a fibrillatable Product, the nature of which is also shown in the following

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Table is given «

The column labeled “Carbowax treatment” in the table indicates the time within which the Carbowax 2OM was added and the subsequent time during which the aisle was stirred. The specification corresponds to 30 minutes of Carbowax treatment of an additional zoite of 4 minutes for the Carbowax 2OM and a subsequent 60 minutes!

development of the melt. I.

λ 1S 2SO 12th D. 15th 2SO 12th C. 30th 280 12th D. 60 280 12th E. 60 280 24 F. 30th 280 24 G 10 260 12th

Example Carbowax · Melting Stirring Speed · Type dos

Treatment temperature strength (U, pM,) fibril Herberen minutes ⁹ C product

PiIn ♦ Pibrils mainly fibrils mainly fibrils perfect 'fibrils Pill ♦ Fibril len There can be fibrils FiIn ♦ some fibr.

From the table above it can be seen that the degree of pi * ball formation, at least in a "polyanide / poly (ethylene glycol) system, depends on three examined variables, well" - I tier "craperatur the Schaelzo, the Ruhr speed and the duration of the Carbowax -Treatment · Thus, a low degree of dsr glasses formation in the fibrillatable product can either be the result of an inadequate mixed treatment (Bei ·· , 'v ?. o'c A i ~ iö G) or an excessive milk treatment with the

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Tendency towards the formation of a homogeneous system (example E). Xn Example A is the poor smearing at the lower temperature of the melt with a corresponding magnification due to the viscosity, which makes the dispersion of the poly * amide in the poly (ethylene glycol) more difficult «

The fibratable products B, D and Fheoen have the following physical properties and chemical properties.

> _ ■ ___. ■■ _ ■

Example Mean Mean Relative Aninend- Carboxylend- Extensibility Tensile strength Viscosity groups groups

long across Grann / Denier (G-Xquiv. (G-Xquiv.

t I long across per million per million

Grief) grief)

B 12.5 16.4 5.44 0.72 43.1 34.3; 66.0

ΧΙΟ " ² Slif ²

D 12.5 12.6 3.81 0.503 61.4 25.8 52.0

^ X10 " ² XiO" ²

F 13.7 16.0 5.48 0.307 48.8 31.1 60 _t S.

x10 " ² ΧΙΟ ' ²

Example 6

A mixture of 1280 parts of poly (hexanethyladipanide), 320 parts of caprolactan and 1000 parts of water was heated in a stirred autoclave in an inert atmosphere until the steam pressure had risen to 17.6 kg / ca ² . The pressure was an hour

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H9455.1

Maintained at this level for a long time and then lowered to atmospheric pressure by venting the Danpf for another hour held for a long time, during which the temperature of the mass rose to 280 ° C. . After 50 minutes at atmospheric pressure, the course of 4 Minutes 350 parts of poly (ethylene glycol) (Carbowax 20M) were added and the resulting mixture was stirred for an additional 26 minutes stirred by an anchor stirrer that made 12 revolutions per minute *

The dispersion of the mixed polyamides was poured onto a stainless-free "i steel existing GleHrad and the band formed · fed through a Ifasserbad a winder The strip was washed in 70 warn to 100 ⁰ C water to remove the poly (8thylenglykol) -Dispersionsmediu" and then dried, 8.2 t of the tape was water-soluble and was removed by "washing" it with the hot water. This low percentage of aiM de "band extractable substance indicates daft a certain amount of poly (ethylene glycol) is chemically bound with the PoIyauidmischpolyaerfibrillen and was not removed by solvent extraction, UEAs presence of Xthergruppen in de" fibrillatable tape lieft by infrared Confirm analysis.

The fibrillatable tape had those listed in the table below physical and chemical properties.

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Medium

Medium

Relative

Arainend- Carboxylend · Extensibility Tensile strength Viscosity groups long cross gram / denier IG-Xquiv. (G-Aquiv

long across per million per million

Graaa) G ram)

17.9 11.7 6.85

0.495 -2

90

35.7

48.0

If the tape is bent over a small radius or over a sharp edge was pulled under tension, it disintegrated into a large number of individual fibrils.

Example Jf

A mixture of 87 g of an elastomeric polyamide, which has been prepared by reacting 240 g of N, N ¹ -diisobutylhexamethylenediamine, and 202 g of caprolactam with 33 g of polystyrene, which is commercially available under the name Bextrene 161, was placed in a glass vessel a nitrogen atmosphere. The heating time was about 30 minutes and after the lapse of this time, the temperature had risen inside the vessel to approximately 200 ⁰ C. A dispersion of the mixed polyamide in the polystyrene was carried out by stirring for 80 minutes with a helical stirrer which carried out 90 cycles per minute. The reaction vessel was then stripped part of the heater away Urd e Ln dor molten dispersion,

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by turning the stirrer over the level of the smoldering in the reaction «· vessel has been raised. The sucked-out tape was then removed from the Stirrer removed and held in a bath containing acetone, which acts as the selective solvent for the polystyrene »If If this band was bent over a sharp edge, it disintegrated into a large number of single fibrils. Those from de «elastoaeren Mixed polyaaid existing fibrils are particularly valuable. fully as a binding agent for fiber tracks, because the activation of the fibrils ,. for example by exposure to heat or a solvent treatment resulting bonds or Pre-bonding lind elastomer. The resulting not interwoven Products therefore have interesting properties, in particular a well-developed drip strength

Example 8

'/ The working cycle described in Example 7 was repeated, with the modification that 33 g of an elastomeric polyester urethane ( were dispersed in 11 g of polystyrene and the mixture a

Heated to 20 ° C for an hour and then with 60 circulations for 8 minutes

was stirred per minute. The fibrillatable product passed from a variety of polyester urethane fibrils and it became produced in that the polystyrene from the soaked

Tape was removed by treatment with acetone. Example, 9 The working groups of Example 7 were repeated with the

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Conversion that 40 g of a polyester urethane in to g of a poly (ethylene glycol) were dispersed and the mixture heated to a temperature of 230 ° C for 45 minutes and then for 15 minutes was stirred at about 20 revolutions per minute. The fibril herable The product consisted of a plurality of fibrils adhered to each other by friction and this was obtained by the polystyrene was removed from the drawn tape by treatment with boiling water.

■ , ■■■ ·

Example 10

The mixture of 1280 parts of poly (hexamethylene adipftmid), 320 parts of Caprolaetaa, 1000 parts of water and 9.4 parts of 20% acetic acid as a stabilizer was heated in an autoclave in an inert nitrogen atmosphere until the vapor pressure reached a value of 17.6 kg / cm ² would have. The mixture was stirred with an anchor stirrer which made 24 revolutions per minute. The pressure was held for 1 hour at that value and then decreased over the course of 1 hour at atmospheric pressure, wherein the temperature of the mixture at 28O ⁰ C rise "After the mixture was maintained at atmospheric pressure for 10 minutes, 500 parts of poly (ethylene glycol) with a molecular weight of

the 6,000 to 7,500, which is commercially available under / designation "Carbowax 6000" and 4 parts of stearic acid were added and the mixture was ^{stirred for 40 minutes at a temperature of 280 0} C .. After the formation of a dispersion, which by the stearic acid acting as a dispersant was supported, the

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Hate poured out on a stainless steel casting wheel, then passed through a water bath and collected as a ribbon. The tape was then washed with hot water, u * the poly * Remove (flethylene glycol) dispersion medium and that itself resulting fibrillatable product was collected.

Example 11

This Example illustrates a continuous process for producing * PolyCepsilon-caprolactam) -FibriIlen that using the in Pig. 1 of the drawing was carried out,

Poly (epsilon-caprolactaa) chips were melted and the melted polymer was added to a reservoir (polymer supply A). From this tank the polymer was pumped at a temperature of 27O ⁰ C by means of a can-0,5 Bemessunge pump at a rate of 16 g / min and supplied to a mixing pump. Before entering the niche pump, the stream of poly (cepsilon-caprolactam) was mixed with a stream of poly (ethylene glycol) which was at a temperature of 100 ° C and was fed from another storage container (polymer supply B) at a rate of 7 g / min. was pumped out by means of a 0.5 ecm rating pump.

Mixing was carried out using a duplex metering pump with an olnom filling volume of 1.5 ecm. In the pump room was a

Dispersion of the PolyCepsilon-caprolactaras) in the poly (ethylene-

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glycol) and then in the pore of a single thread * through a Pressed opening, which juiced a diameter of 0.5 mm. The monofilament was washed with hot water in order to Remove glycol dispersion medium and the remaining fibrillatable tape was collected on a spool.

Some physical and chemical properties of produced by this continuous process of fibrillatable process f Dukten using Paly (epsilon-caprolacta ") / poly (äthylsnglykol) fiber-forming with various amounts of Poly * (epsilon-caprolactam) are together in the following table * posed.

% Carbouax Relative Aminend- Carboxyl- t Hasser Pestig- t

Viscosity group end group extraction Extra ·

bar gram / here denier bar

30 28.2 49.5 33 29.5 0.60 5.5 33.333 28.9 50.8 34 27.9 0.59 4.8

In the continuous process, the degree of blending of the two polymers for optimal results is the same important as in the autoclave process. Another factor that is Aryan is essential for the achievement of good results, is the shear rate applied to the extended mass.

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A fibrillatable product made from PolyCepsi & on-caprolacta «) pulled over a sharp edge, turning it into a frost Selection of pibrils made of poly (epsllon-eaprolactaa) «granted · 2 g of these pibrils were dispersed in 1400 cc "cold" water, which contained a few drops of Oispersol VL as a wetting agent «

The sludge was passed through a sieve with a mesh size of 0.076 m filtered, so that a leaf moist with water remained. This The sheet was cut into 1.27 χ S cn large strips and opened in terms of tensile strength when it was still moist on an Instron tensile testing machine

The following results were obtained.

Sample tensile strength Extensibility Graaa / Denier in percent

1 2.16 X ίο "* 10.8 2 2.46 X ίο "* 8.0 S. 1.75 X ίο ** 12.8 4th 2.16 X ίο "* 7.6

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The process forming the subject of the invention is different take advantage of some other procedures sur her * position of fibril-producing products with regard to its application to polymer systems, which are a major part of contain a fiber-forming polymer, indea this fibrillable products are obtained from which by simple Seam tone fibrils can be obtained without removing the product must be subjected to a special stretching treatment

PATENT APPLICATION:

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Claims (10)

U9A551 Claims ι l.j method for making a fillable Structure, characterized by the fact that one is a dispersion a fiber-forming synthetic polymer as a disperse Phase in a synthetic polymer other than Disperäons- Ä medium, the dispersion medium 1 - 48 Gew .- ^, based on the Gewloht of the two polymers Dispersion, matter, this dispersion eXtruded and then from the Extrudet as a dispersion medium serving synthetic polymer removed 2. Process for the production of a structure that can be formed, characterized by the fact that a dispersion of a fiber-forming polymer as a disperse phase In another polymer as a dispersion medium " represents, wherein the dispersion medium 10-40 wt. ~ £ · based on the weight of the two polymers of the dispersion, makes up, this dispersion extrudes and then from the Extrudate the synthetic one serving as the dispersion medium Polymer removed. 3. Process for the production of balls, daduroh characterized in that one disperses a faaerbildexftn - 46 - 909832/127 / »' BATH ORIGINAL U94551 Polymers as disperse phase In a different polymer than DiBporslonsmedium produces »whereby the Disperalonsmedlüm 1-48 Oetr * <· »£, based on the Qewloht of the two polymers the dispersion, makes up, this dispersion extruded, from the extrudate serving as the dispersion stage synthetic polymer is removed and the resulting fillable structure dissolves. 4. The method according to claim 2, characterized in that ι that the fiber-forming synthetic polymer of the disperse phase is selected from the group of condensation and Addition polymers consists. 5. The method according to claim 4, characterized in that that the fiber-forming synthetic polymer of the disperse phase is selected from the group consisting of polyamides, N ~ 8 substituted polyamides, polyesters and polyurethanes consists. 6. The method according to claim 5, characterized in that the fiber-forming synthetic polymer of the disperse Phaso selected from the group consisting of polyhexamethylene adlpamid » Poly-epsilon-caprolaotam, Polyhexamethylenadlpamld / Poly-epsilon-caprolaotamoMlsohpolyiaeren . and polyethylene terephthalate * - 47 ^1909832/1274 BAD ORlGlHAL U9A551 7. Process according to Anepruoh S or 3 » characterized in that the synthetic polymer of the dispersion medium can be selected from the group consisting of polyethylene glycol and polystyrene. 8 «Procedure naoh Anepruoh 8 or 3 * thereby identified · «« Rejects that the dispersion polyhexaethylene adlpamld as disperse phase and polyethylene glycol as dispersion medium contains. 9 · Procedure naoh Anepruoh 2 or 3 «thereby identified · ■ calculates that the dispersion is poly (ethylene terephthalate) disperse phase and polyethylene glycol as Dlsperelon " ■ edlusi contains. 10. Procedure according to Claim 1, thereby being recognized » that the dispersion of a polymer in the other with the help of a pump is effected. PATEN rA.V. DUNG, a FIUCKE DIPL-ING. R DRILL DlPC-ING. Ι.8ΤΑΕΟβ C ORIGINAL Blank page