WO2006006066A1

WO2006006066A1 - Thermoplastic, thermally bondable polyolefin fibre for production of nonwovens as well as a nonwovens obtained by thermal bonding

Info

Publication number: WO2006006066A1
Application number: PCT/IB2005/002010
Authority: WO
Inventors: Felice Polato; Giampaolo Guerani
Original assignee: Saurer Gmbh & Co. Kg
Priority date: 2004-07-07
Filing date: 2005-07-05
Publication date: 2006-01-19
Also published as: BRPI0513138A; CN1993505A; EP1781846A1; ITFE20040012A1; US20080057308A1; RU2007104327A

Abstract

The invention relates to a thermoplastic, thermally bondable polyolefin fibre for production of nonwovens as well as a nonwovens obtained by thermal bonding of such polyolefin fibres. The production of nonwovens for applications in hygienic end uses have thermal bonding and softness characteristics dependent on the fibres. For improvement the fibre of the invention shows a whole plastic deformability under calendaring process in the thermo-bonding dot and a low surface degradation during spinning. Therefore the thermobonding dots of a nonwovens are characterised by the whole close packing of the fibres. The thermal bonding behavior of the fibre will be reach with a spinning process with spinning head temperature set up suitable in order to obtain the specified thermal degradation.

Description

"Thermoplastic, thermally bondable polyolefin fibre for production of nonwovens as well as a nonwovens obtained by thermal bonding"

FIELD OF THE INVENTION

The invention relates to a thermoplastic, thermally bondable polyolefin fibre for production of nonwovens as well as a nonwovens obtained by thermal bonding of such polyolefin fi¬ bres.

BACKGROUDOFTHEINVENTION

Polyolefin fibres and, more specifically, polypropylene fibre as themselves or in blend with other fibres like wool, cotton, polyester, are widely used for the production of several arti¬ cles with different morphology.

This usage has been remarkably improved by several characteristics of these fibres like high chemical inertia and absence of polar groups, no toxicity and cytoxicity, low specific weight, low thermal conductivity and high insulating power, high abrasion resistance, high mildews and bacteria resistance, high colour fastness and, last but not least, easy proc- essability and low cost.

Textile (underwear, sportswear), floor coverings (carpets), industrial and hygiene are some of the most important applications which have been developed on the basis of one or more of the above mentioned fibre behaviours.

It is well known that polyolefin fibres and, more specifically, polypropylene fibre, are pro¬ duced by the melt spinning technology which consists in melting the polymer at high tem¬ perature in one extruder. The melted polymer is afterwards forced to pass through a spin¬ neret mainteined at controlled high temperature.

In order to obtain some important additional behaviours on the fibre, specific chemicals are added to the polymer before or during the spinning step:

^■ stabilizers (process stabilizers, anti-oxidant etc.)

^■ coloured pigments

^■ optical brighteners to improve the whiteness

^■ matting agents to modify the transparency

After the exit from the spinneret, the hot spun filaments are quenched by air and undergo the subsequent processing steps of drawing, crimping, drying to reach the final cohesion and mechanical characteristics required by the following fibre processing. The fibre obtained by the above mentioned steps is afterwards cut and baled. Specially tailored spin finish formulations are applied during some steps of the production process to give to the fibre the antistatic, lubricant and cohesion characteristics necessary for the processability. Furthermore the above spin finish formulations must impart to the fi¬ bre the additional hydrophilic or hydrophobic behaviours required by the end use.

Several different morphologies and structural compositions are shown by prior art polyole- fin fibres for thermal bonding:

Bicomponent fibres like sheath - core o side by side disclosed for instance in US 4,473,677, US 5,985,193, WO9955942 or US 5,460,884.

These fibres are obtained by using two extruders separately feeding two different polymers (i. e. : polypropylene/polyethylene or polypropylene/polyolefin copolymer) to specially designed spinnerets through separate gear pumps.

Structural bicomponent or "bicostituent" constituted by blends of polymers directly obtained inside the spinning extruder as disclosed for instance in US 5,985,193, WO9955942 or US 5,460,884.

"Natural" bicomponent showing a "skin-core" morphology and obtained from single polymers or from blends of polymers by the use of special conditions of the spinning and quenching steps of the production process which lead to the formation of a de¬ graded skin on the fibre as disclosed for instance in US 5,281 ,378, US 5,318,735, US 5,431 ,994, US 5,705,1 19, US 5,882,562, US 5,985,193 or US 6,116,883.

The above mentioned patents and patent applications assert that the achievement of the bonding behaviour of the skin-core fibres is due to the formation of a degraded skin and claim that such a skin is always obtained by the use of suitable processing conditions.

On the contrary it will prove that, in absence of a specifically tailored polymer stabilisation, the thermal bonding behaviour of these fibres may be poor because of an excessive or, on the contrary, limited degradation of the polymer. The main constraints of prior art are for long spinning process the nonwovens limited softness and for short spinning process the nonwovens low tenacity.

SUMMARY OF THE INVENTION

It is therefore an object of the invention to create a thermal bonding fibre for high non¬ wovens tenacity, which allows a wider process operating window and better control of the quality consistency of the fibre and the nonwovens.

An other object of the present invention is to solve some main constraints in the thermo- bonding process versatility and nonwovens quality when standard homo-PP fibres are used, from both long spinning or short spinning process.

In accordance with the invention, this object is accomplished by the thermoplastic, ther¬ mally bondable polyolefin fibre with the features of claim 1 , the spinning process of such a polyolefin fibre with feature of claim 7 and the nonwovens obtained by thermal bonding of such polyolefin fibres with feature of claim 9.

The present invention wants to combine the welding effect due to the enhanced plastic behaviour of the fibre together with the effect of the minimal useful thickness of the weld¬ ing skin. The invented fibre shows a very low surface degradation during spinning and a whole plastic deformabilility after calandering under pressure. Therefore the thermobond- ing dots in a thermobonding nonwovens are like a thin and homogeneous polymer foil. All the fibres are loosing their single identity and are welded completely together to the ther¬ mobonding dot. In the area of forced contact under the calendar compression the fibres show a complete melting and molecular interpenetration of the surfaces.

For production of such a fibre a spinning process is proposed wherein the spinning head temperature set up suitable in order to obtain the specified thermal degradation of the fi¬ bre.

The invented nonwovens obtained by thermal bonding of said fibres show a higher tenac¬ ity in comparison to prior art due of whole close packing of the fibers in the thermally bonded dot.

By such a technique the following advantages of the invention are realised:

■ the operating window of the spinning process becomes remarkably wider thus improv¬ ing the quality evenness of the fibre

■ a tailor made optimisation of the non woven characteristics becomes feasible by fa¬ vouring the tenacity or the softness or intermediate combinations

To realise the above targets it's necessary to utilise polymeric systems in which it might be possible to enhance the plastic deformability phenomenon during the calendering stage. In the second instance the additive formulation of the polymer must allow the formation of the minimal useful thickness of skin.

With reference to the analytical problems concerning the determination of the depth of the skin really usable in the welding process, the field of the values of the Degradation Index (Dl) lays between 1 ,50 and 3,0 depending on the characteristics which are selected as targets on the nonwovens. The degradation index Dl is the value of the ration between the fibre melt flow rate and the resin melt flow rate as will be described in detail later on. Espe¬ cially good effects during thermobonding good be reach with a degration index Dl in the range of 2,0 and 2,5.

As previously mentioned, in order to achieve the plastic deformability, it's necessary to add structural disorder to the crystalline phase to allow an easy trigger of the molecular sliding under stress.

Among the possible polymeric system combinations, the followings may be mentioned as no limiting example:

- PP + PP/PE + PP/PB

■ PP + PP/PB

■ PP + PP/PB/PE and, also, all the other combinations containing an high crystallinity homo or copolymer as base, one or more components constituted by homopolymer PP or copolymer PP/PE and an additional component constituted by copolymers of PP or PE with α-olefins character¬ ised by a structure with limited crystallinity. The weight proportion of the blend could be in the range between 0% and 90% homopolymer and between 100% and 10% of PP-oc-olefin copolymer .

All the above components must show a total miscibility among them in order to assure a good processability during the spinning stage.

An important characteristic of the above copolymers is the melting temperature of their polypropylene crystalline phase which, generally, is inversely proportional to the content of comonomer ("Polypropylene Handbook", edited by Edward P. Moore, Jr. , 1996. Chapt. 6.3.2, fig. 6.6).

For better clarity, furthermore, it can be outlined that a lower melting temperature of crys¬ talline PP corresponds to a lower binding energy of the crystallite itself and this fits per¬ fectly with the previously mentioned concept of easier plastic deformability.

In fact, the invention is concerned with the spinning process of PP fibre by doling out the skin degradation and by using the plastic behaviour of some blends of polymers. The above target is achieved by using specific set up solutions for:

^■ additive formula

^■ raw material blend

^■ process conditions

More in particular, the dosing of the fibre skin degradation is controlled by the additive formula and by suitable process conditions. A raw material containing primary antioxidant in the range between 150 ppm and 600ppm leads to good degradation control. By using specific raw material blend, the thermoplastic behaviour of the fibre in the cal¬ endering plant is optimised . in order to achieve the top of tenacity by also controlling tem¬ perature and pressure of the rolls.

Process conditions in the fiber producton and in the following calendering.thermalbonding step are driven according to the raw material formula and characteristics. In such way, the tenacity-softness can be taylored according to the final applicative need.

Taking into account the poor thermal conductivity of polyolefins, together with the very short residence time of the fibre into the calendering treatment, the thermoplastic behav¬ iour of semi-crystalline polyolefins can assume the dominant role during thermal bonding step in calendering machine. BRIEF DESCRIBTION OF THE TABELLES AND FIGURES

Fig. 1 : Thermal bonding model for skin-core fibres prior art

Fig. 2: Nonwovens bonding dot after calendaring prior art fibres

Fig. 3: Thermal bonding model for fibres according invention

Fig. 4: Nonwovens bonding dot after calendaring fibres according invention

Tab. 1 : Influence of the spinning temperature on fibre degradation (MFR) and nonwovens

Tab. 2: Influence of the stabilization formula on PP thermal stability and thermal oxidative stability of polypropylene

Tab. 3: Influence of the polymer blend composition and degradations index (Dl) on fibre thermal bondability

DETAILED DISCRIPTION OF THE INVENTION

The plastic behaviour of the polymer is the capability to withstand large deformations (until

600-700% in some cases) and to retain the deformed shape after removing the deforming stress. In such deformation process, two different steps are recognised.

In the first step, below 1 %, the deformation is elastic and reversible with the applied stress. During the elastic deformation, some temperature decrease can be observed in the body.

In the second step, over the elastic limit, the deformation become plastic or irreversible and the relative flow of material in the body is observed. The molecular friction due to the above flow can produce increase of the body temperature if the deformation process is fast enough in reference to the heat dispersion effect due to the thermal conductivity of the material.

In the calendering process of the nonwoven web, the material plastic behaviour can play active role in the thermal bonding result if a wide plastic deformation of the fibre section is carried out in the suitable way. To this purpose, the following main actions are required:

■ in the spinning plant, use of the suitable polyolefin raw material (containing molecular disorder in the crystalline phase)

■ in the calender plant, increase pressure and, if required, decrease temperature of the rolls.

Concerning the molecular disorder, it has to be considered that such areas can be the starting point for the molecular plastic flow under external stress. In fact, they are areas where the bonding energy of the crystalline building is lower. PP homopolymer can be disordered in different ways when crystallinity is high. One of the more straight ways is by blending to PP homopolymer some quantity of compatible polyolefin copolymer between PP and (α-olefin) co-monomer, where the (α-olefin) co- monomer is below 10%. The effectiveness of the above solution is explained by the disor¬ der effect of the (α-olefin) chain segment during crystallisation of the PP chain.

It follows from the above discription that the thermal bonding mechanism of polyolefin fi¬ bres is the result of the presence of the degraded skin and of the plastic behaviour of the fibre section under mechanical stress.

The fibre bonding mechanisms like prior art is using skin-core PP-fibres. Such skin-core PP fibre is widely used in thermal bonding as known. The main feature of the above fibre is the difference in melting point between skin and core. More in particular, being the skin degraded in molecular weight, its melting point is lower in comparison to the high molecu¬ lar weight core section. In more detail, during the calendering action, when the skin layer is quite in molten state, the core of the fibre is still solid. Following the above considerations, the thermal bonding model with skin fibres according prior art can be outlined as in Fig. 1 , where it is shown:

■ under the hot roll compression, the single fibre aims to keep its original circular section

■ the roll compression is putting close together all the fibre and the skin layer is molten firstly, so flowing into the residual free volume between the fibre and like a glue.

■ after very short time (10 milliseconds about) the compression effect is ended and the fibre assembly aims to re-arrange its position under the residual elastic effect, until the solidification of the molten skin layer. During such re-arrangement the "glue" is stretched and tends to form bridges of membrane and/or filaments between neigh¬ bouring fibre, as shown in Fig. 2. Of course, quantity and size of the bridges are de¬ pending from many process variables (thickness and quality of the skin, temperature, pressure, speed, etc).

■ as for confirmation of the individual core keeping by the single fibre, in spite of the compression stress applied on the dot during calendering, it can be seen (Fig.2) that the single fibre is visible also in the fibre intersection zone, in spite of the compressive stress applied.

With the invented fibre, object of the present invention, apart the possible presence of de¬ graded skin, the thermal bonding model is outlined as in Fig. 3, where it is shown:

■ the single fibre, under the roll compression in calender, is loosing quite completely the original circular section and id deformed in order to allow the fibre close-packing. In such volume arrangement, all the fibre are loosing also their single identity and the welded dot becomes like a thin and homogeneous polymer foil.

■ as shown in Fig. 3, fibres are closely packed and, even if degraded skin is present, number and size of "glue" bridges between neighbouring fibres is very low.

■ it is crucial to note that, as first result of the high plastic deformability of the fibre sec¬ tion, the strong thermal bonding effect is obtained with the minimum thickness of de¬ graded skin. » as shown in Fig. 4, the welding dot is well homogeneous. With the naked eye, the welding dot appears to be transparent due to the optical homogeneity in the polymer bulk..

The presence of crystalline disorder in polymers can be observed by Differential Scanning Calorimetry (DSC) analysis, where it is measured the enthalpy of fusion and the melting temperature.

In this analysis, a blend made by PP homopolymer and PP-PE random copolymer shows its melting temperature in between the two components and more close to PP, not just in the middle according to a linear low of just blending.

This effect is well explained by assuming that, in the solidification process of the blend, the two components are included by a unique crystalline phase having a unique melting proc¬ ess. The lower value of the melting temperature of the blend in comparison to the pure homopolymer means a lower binding energy of the crystalline phase, according to the known theories of the polymer physics. Of course, the inclusion of the copolymer into the homopolymer crystallline building, because of the different molecular stereo-regularity, causes the disorder effect during the blend solidification.

In a different technique, X-ray diffraction (XRD), the crystalline disorder of polymers can be observed in terms of:

- variation of crystal planes distance

- crystal plane completeness

On molecular scale, crystalline disorder means "displacement/insertion of atoms/chain segment in the crystalline lamella of PP. As a matter of fact, for example, the PP-PE ran¬ dom copolymer with low content of PE can be considered as imperfect PP where the chain segments of PE are forced to stay inside the PP crystalline building during solidification, so creating disorder and reducing number and energy of the molecular bonds in the solid. This is the reason why also pure polyolefin random co-polymers are suitable resins for the plastic thermal bonding effect. On the other hand, polyolefin blend can be more suitable than pure copolymers for the flexibility of the fibre bulk characteristics.

The production of calendered nonwovens from fibre staple is carried out several days after the fibre spinning. It is a good cost saving tool to test the staple thermal bondability just after the spinning, before packaging.

To this purpose, it has been developed the lab test W.I. (Weldability Index, by F. Polato, private com, Nov. 30, 1998)

In the method, few grams of staple are carded. The small web is submitted to compression load at high temperature for a short time. The tenacity of the thermally bonded web is measured.

By using controlled conditions for all the steps, the test results are closely related with the tenacity of the industrial nonwovens. Different spinning technologies can be used for industrial production of polyolefin staple fi¬ bres. Today, the most widely used are usually known as "long spinning" and "short spin¬ ning".

The two technologies are different for both technical and economical factors. The usual trend for plant set up is looking for the skin-core fibre with the following characteristics:

■ the skin is the external layer of polymer degraded by thermal-oxidation (chain scis¬ sion) where:

- the average MW is very much lower than in the starting resin

- the MFR is much higher than in the core of the fibre

- the melting temperature is clearly lower than in the starting resin

■ the core of the fibre is the internal remaining section, and is quite unchanged in com¬ parison to the starting polymer.

In fact, after the hole spinneret, the fibre at high temperature is immersed into air and the oxidation process starts immediately from the fibre surface and penetrate the fibre in ra¬ dial direction. The oxidative degradation of PP, as known, is a chain scission process in which the polymer molecular weight is reduced.

The target is to achieve the lower melting temperature and the suitable thickness of the skin, in order to obtain the highest tenacity in calender plant with the minor roll tempera¬ ture.

As matter of plant experience, the degraded skin having the right quality for the high te¬ nacity of the thermally bonded nonwovens is obtained only in a narrow range of spinning temperature (see Tab. 1). The most important process conditions for quality and thick¬ ness of the skin are:

■ polymer temperature out of the hole spinneret (high temperature inside the spinning line are ineffective

■ air quenching flow, in terms of thermal capacity flow, for the freezing effect of the ther- mal-oxidative degradation by decreasing the fiber temperature.

The "thickness" of the degraded skin is the result of interaction between the temperature of the fibre leaving the hole spinneret and the time at high temperature available to oxygen for its central diffusion in the fibre itself.

In other words, the thermal-oxidative process for the formation of the skin is controlled by two minimum threshold: temperature and time

Concerning time, the two technologies above mentioned allow similar residence time of the fibre at high temperature (10 milliseconds is the time magnitude order). On the other hand, it is well known that the short spinning technology don't allow the skin degradation of PP in easy way. For this, it must be taken into account that short spinning technology must use high speed quenching flow and very close to the spinneret holes. The final effect is the lower temperature of the fibre in output of the spinneret and the degradation kinet¬ ics lower speed.

In addition, commercial grades of PP for fibres are containing heavier additive formulas, optimised in long spinning technology, where the thermal-oxidation reaction is easier. Further on, it must be related the thermal-degradation process for the skin with the final characteristics of the nonwovens.

In Tab. 1 it is shown the "fibre MFR" and "nonwovens tenacity TBI" versus the spinning head temperature, all the others process conditions kept constant. Firstly, polymer degradation (MFR) is growing slowly with the temperature increase, until the "threshold" value of 280⁰C. Over the threshold, the degradation process is accelerated more and more. At the same time, the nonwovens tenacity starts to improve at 280⁰C, reach the peak value at 290° and after decreases in spite of the increase of degradation above mentioned. Of course, the relationship is depending quantitatively from plant type and ad¬ ditive formula.

From Tab. 1 the standard process dynamics can be explained as follows. Until 280⁰C of spinning head temperature, skin degradation does not take place on the fi¬ bre.

Over this threshold, the degraded skin layer is growing in thickness with exponential law versus temperature. Of course, the increase of skin thickness means that degradation is proceeding versus the middle, so reducing the size of the residual unchanged core and, at the same time, the tenacity of the fibre. For very high spinning temperatures, the fiber thermal bondability would be excellent but, because of the very poor mechanical charac¬ teristics of the degraded fibre, the nonwovens tenacity is worst.

From all the above points, it can be concluded:

■ the skin-core structure can be obtained only over the temperature threshold

■ the spinning temperature operating window for the highest nonwovens tenacity and by using PP homopolymer and standard spinning technology is narrow (only few de¬ grees)

Moreover, taking into account the interactions of the several variables, some compensat¬ ing effect can be used for plant set up among:

- spinning head temperature

- quenching flow temperature

- quenching flow speed

- distance between spinneret surface and upper surface of quenching flow (=quenching distance)

In fact, the above variable are inter-dependent for the skin formation. In particular, for the same additive formula, the set up of the above variables allows the control over the amount of skin quantity and quality.

Other useful comments are:

- over its minimum threshold, the spinning head temperature is dominant for the skin control

- below, the skin is undetectable far over the threshold, the nonwovens tenacity is worst the amount of antioxidant additives in the polymer recipe is dominant for the skin deg¬ radation. More in particular, for skin degradation in short spinning lines, the antioxidant level must be low. optimal thickness and low melting temperature of the skin are required for the high te¬ nacity of the thermally bonded nonwovens obtained from skin-core PP fibre (see model of Fig.1) for high tenacity of the thermally bonded nonwovens obtained from plastic PP fibre, the skin thickness required is much lower than with skin-core fibre (see model of Fig.3)

For the detection of the skin in PP fibres, some test methods have been considered:

■ optical microscope analysis of the silicon oil ultrasonic extract of the fiber at high tem¬ perature (Takeuchi et al. USP 5,705,119; Jan. 6, 1998)

■ TEM analysis of the fibre section previously stained by RuO4 (Trent et al, Ruthenium tetra-oxide staining of polymers for electron microscopy, Macromolecules, vol 16, No. 4, 1983).

Unfortunately it was found that the two test methods are unreliable for analytical use be¬ cause none close relationship was shown among test results and thermal bondability of the PP . On the other hand, it is well accepted that the welding skin is formed on the fibre surface during spinning and because of degradation by chain scission.

Following this concept, it can be shown the close relationship between nonvowen tenacity (TBI) and the Degradation Index (Dl) of the polymer during spinning.

Definitions

(1) TBI = SQRT (CD * MD)) * 20/W

(2) Dl = ( MFR fibre)/( MFR resin) where: CD = cross direction tenacity of the non-woven

MD= machine direction tenacity of the non-woven

W = weight of the non-woven

MFR = polymer fluidity according to ASTM D-1238-L

Of course, the above close relationship can be obtained by keeping constant the calen¬ dering process set up and the resin spinning process, being the spinning temperature variable. In such configuration, the degradation effect (Dl) is the straight effect of the spin¬ ning temperature.

The following are first references:

- Dl = 1 ,0 is the lower limit (theoretical) with lack of any degradation

- 1 ,5 < Dl < 3 is for intermediate degradation and partial skin formation

- 3 < Dl < 4 is the range of typical skin core commercial fibres - Dl > 4 is for excessive degradation, fragile fibre and worst non-woven tenacity

With reference to the thermal bonding mechanism (Fig. 3,4), if the fibre plastic behaviour in calender is suitable, it is found:

- higher tenacity of the nonwovens for the same Dl value in comparison to skin-core homo PP fibre

- high tenacity of the nonwovens also for low Dl values, corresponding to low skin pres¬ ence.

The additive formulation of the polymer is an essential feature as it controls, by definition, the polymer degradation mechanism. Such a control becomes particularly effective on the outer layers of the fibre at the exit of the die when the hot polymer gets in touch with the oxygen of the atmosphere.

The additive formulation of the polypropylene fibre for non wovens in the hygiene applica¬ tions is generally studied on the basis of the main degradation mechanisms deriving from: a) oxygen at high temperature b) high processing temperature in absence of oxygen c) long storage time (shelf life)

The protection to oxygen at high temperature is generally carried out by primary anti oxi¬ dants like sterically hindered phenols (C.A.S. Nos. 6683-19-8, 27676-62-6, 2082-79-3 and others), afterwards reported as AO1 or by more recently developed additives like lactones (C.A.S. No. 181314-48-7 and others) afterwards reported as AO2.

The protection to the high processing temperature in absence of oxygen is generally car¬ ried out by secondary anti oxidants like organic phosphites (CAS Nos. 31570-04-4, 119345-01 -6 and others) or organic phosphonites (CAS No. 119345-01 -6 and others) in combination with AO1 or AO2.

The protection to long storage time (shelf life) is assured by both AO1 and sterically hin¬ dered amines (polymeric HALS; CAS Nos. 71878-19-8, 106990-43-6 and others).

Among the above mentioned mechanisms, the most important one is that which controls the thermal oxidative degradation of the polymer at high temperature. More specifically, the thermal oxidative mechanism must be quantitatively controlled to obtain the required thickness of degraded skin.

In other terms, as the degraded and low melting point polymer has insufficient mechanical characteristics, it is necessary to dose the thermal oxidative degradation to reach the minimal useful thickness of degraded skin. An excessive degradation leads to an increase of the bonding skin but the mechanical characteristics of the non woven become worse as also the core of the fibre undergoes degradation (see table 1). In order to get the properly dosed thermal oxidative degradation, according to the present invention, the concentration of primary anti oxidants must be between 150 ppm (highest degradation) and 600 ppm (lowest degradation).

T.O.S.I. (Thermal Oxidation Stability Index, "F. Polato: comunicazione privata Nov. 30,

1998") represents a very effective testing method to separately and jointly evaluate the stability of polypropylene to oxygen at high temperature and to the high processing temperature in absence of oxygen.

This method assumes that the MFR, as it is well known, is a good indicator of the average Mw and it's based on the evaluation of the molecular degradation of the polymer as a consequence of:

- exposure to a constant temperature and for a defined time in a closed cell, in absence of oxygen

- exposure to a thermal oxidative action by extruding the polymer at high temperature in presence of oxygen

A common instrument for the measurement of MFR is used for the above trials.

As it is shown in Table 2, different additive formulations of the polymer lead to a remark¬ able difference of the degradation at high processing temperature in absence of oxygen and of the thermal oxidative degradation (Formulations 1 , 2).

In the mean time, certain additive formulations may show very similar levels of thermal oxidative degradation and a noticeable difference of the stability to the high processing temperature in absence of oxygen (Formulations 1 , 3).

Polyolefin homopolymers and copolymers like PP and PE are widely used for the produc¬ tion of thermally bondable fibres for non wovens in the hygiene applications. .

PE homopolymer, nevertheless, shows some important limitations as far as price and te¬ nacity of non woven are concerned, even if its relevant contribution to the softness of the non woven is well known

The use in low concentration of other polymers as ethylene copolymers containing polar monomers like vinyl acetate, methyl-metacrylate and others, blended with polyolefin ho¬ mopolymers and copolymers, is reported several times in the existing patent documenta¬ tion. The use of such polymers in the real industrial practice is, nevertheless, very limited due to several factors like:

■ price of the raw material

^■ compatibility limits with polyolefins leading to troubles during the spinning process

PP homopolymer shows, therefore, the major interest for the production of staple fibres for non wovens in the hygiene applications due to the following reasons:

■ lower cost of the raw material

■ good processability

^■ satisfactory tenacity behaviour of the non woven

On the other hand, the thermal weldability of the PP homopolymer fibre is due to the de¬ graded skin which is formed during the spinning according to the process stages previ¬ ously reported.

Polymers different from homopolymer PP (with the exclusion of bicomponent sheath - core fibres obtained by feeding the spinneret with two different polymers) are used only in the cases in which there is the will to improve the softness.

Even in such cases, as well as in the case of the use of homopolymer PP, the spinning process is performed in a way to optimise the formation of the skin to reach the highest te¬ nacity of the non woven. The above mentioned limits of this technology are still existing in any case.

In Table 3 the results obtained by experimental spinning trials done on a NEUMAG spin¬ ning line.

2,2 dtex / 40 mm. cut length PP fibres have been produced by adopting several polymeric compositions and by keeping constant all the process parameters with the exception of the spinning head temperatures.

These temperatures have been specially tailored to reach well defined levels of Dl value on the spun fibres.

The weldability of the fibres has been afterwards measured by the W. I. testing method

Results may be summarised as follows:

■ in absence of both the welding mechanisms (fibre plastic behaviour and presence of degraded skin), a 100% homo PP fibre with a Ql < 1 ,50 shows a very low value of W I. (test nr. 1)

■ in presence of the sole plastic behaviour mechanism (obtained by the use of increasing quantities of raco PP in the polymeric formulation), PP fibres with a Dl < 1 ,50 show W. I. values which increase accordingly to the concentration of raco PP till reaching high levels of weldability (tests 2-8) when both welding mechanisms are present in the fibres (plastic behaviour and pres¬ ence of degraded skin with a Dl > 1 ,50), the fibres themselves reach very high values in the W. I. test .(tests 9,10).

Tab. 1 : Influence of the spinning temperature on polymer degradation (MFR) and non-woven

Tenacity (TBI) spinning temp. fibre MFR non-woven TBI

⁰C g/10 min N/5cm

270 10,1 11 ,5 275 11 ,1 12,4 280 14,3 14,3 285 23,4 19,6 290 36,0 24,8 295 49,5 19,6 300 64,0 11 ,7 305 68,0 10,8 310 73,0 9,8

Tab. 2 : Influence of the stabilization formula on PP thermal stability and thermal oxidative

stability of polypropylene

formula AO1 AO2 total additives MFR TSI OSI ppm ppm ppm g/iu mm

1 150 1150 10,2 1 ,40 12,5

2 250 1700 10,2 1 ,14 10,2

3 150 1250 10,2 1 ,05 12,2

where:

- MFR = starting fluidity of the polymer

- TSI = thermal stability index

- OSI: = oxygen stability index

Tab. 3 : Influence of the polymer blend composition and degradability (Dl) on fibre thermal bondability (Wl)

blend composition (%) Dl Wl n. test PP homo PP/PE raco

1 100 0 1,30 370

2 90 10 1,31 510

3 80 20 1,32 780

4 70 30 1,32 900

5 60 40 1,33 1150

6 50 50 1,36 2600

7 40 60 1,37 3900

8 20 80 1,41 7800

9 60 40 1,9 2100

10 60 40 2,3 4050

11 60 40 3,1 13000

where:

Dl = degradation index Wl = weldability index

Claims

1. Thermoplastic, thermally bondable polyolefin fibre, suitable for production of nonvowen, characterized by whole plastic deformability under calandering process in the thermo- bonding dot and by a low surface degradation during spinning.

2. Fibre of claim 1 characterized by the ratio of the fibre melt flow rate (MFR fibre) to the resin melt flow rate (MFR resin) with its value Dl (Dl = (MFR fibre)/(MFR resin)) in the range between 1 ,5 and 3,0.

3. Fibre of claim 2 characterized by a value Dl of the ration (MFR fibre)/ (MFR resin) in the range between 2,0 and 2,5.

4. Fibre of claim 2 or 3 characterized by made of a first component PP homopolymer and, at least a second component, blend compatible with the first and composed of PP co¬ polymer with at least one <^χ-olefin co-monomer.

5. Fibre of claim 4 characterized by a weight proportion of the blend in the range between 0% and 90% of PP homopolymer and between 100% and 10% of PP-oc-olefin co¬ polymer.

6. Fibre of claim 2 to 5 characterized by a raw material containing primary antioxidant in the range between 150 and 600 ppm.

7. Spinning process of polyolefin fibres made according to claims 1-6 characterized by a spinning head temperature set up suitable in order to obtain a thermal degradation of fibres, so that the ratio of fibre melt flow rate and resin melt flow rate (MFR fibre)/(MFR resin) has a value Dl in the range between 1 ,5 and 3,0.

8. Spinning process of claim 7 characterized by a quenching flow temperature or a quenching flow speed or a quenching distance or a combination of quenching variables suitable to obtain a very low skin degradation at the fibre.

9. Nonvowen obtained by thermal bonding of polyolefin fibres made according to claims 1 -6 characterized by the whole close packing of the fibres in the thermally bonded dot after calendering under compression due of the whole plastic deformability of the fibres.

10. Nonvowen of claim 9 characterized by a thermal degradation of the fibres by spinning in the higher range of the value Dl between 2,5 and 3,0, wherein the best softness is obtained by reducing to the minimum allowed calender temperature.

11. Nonvowen of claim 9 characterized by a thermal degradation of the fibres by spinning in the lower range of the value Dl between 1 ,5 and 2,0, wherein the best softness is obtained by increasing the calender temperature until the required tenacity. 2. Nonvowen of claim 9 characterized by a thermal degradation of the fibres by spinning in the higher range of the value Dl between 2,5 and 3,0, wherein the highest tenacity and the best softness are obtained by increasing the calender temperature.