CN101341177B - Soft non-woven fabrics - Google Patents
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- CN101341177B CN101341177B CN2006800483890A CN200680048389A CN101341177B CN 101341177 B CN101341177 B CN 101341177B CN 2006800483890 A CN2006800483890 A CN 2006800483890A CN 200680048389 A CN200680048389 A CN 200680048389A CN 101341177 B CN101341177 B CN 101341177B
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Abstract
Soft filaments and spunbonded non-woven fabrics obtained therefrom are provided, said filaments comprising a blend of a propylene copolymer or a propylene copolymer composition and an heterophasic propylene polymer composition.
Description
The present invention relates to can be with the propene polymer long filament of excellent spinning property preparation and fiber with by the soft nonwoven of its acquisition.Known alfon has excellent spinning property in this area, but because their fusing point is higher, promptly typically up to 165 ℃, they need high temperature to be used for through thermal process such as the spunbond preparation non-woven fabrics of heat.In addition, the fiber that is obtained by alfon has the feel of being on duty mutually with non-woven fabrics.Important role is being played the part of in the feel of fabric or sense of touch, because there is the demand for the growth of " soft feel " non-woven fabrics on the market.Propylene copolymer and prolylene polymer composition can be used to overcome the defective of alfon expediently.
For example, International Patent Application WO 2004/029342 discloses the non-woven fabrics that comprises crystalline propylene random copolymer or crystalline propene polymer composition, and wrinkling said crystalline propylene copolymer or compsn have good thermal cohesiveness.European patent EP 663965 discloses and has comprised alfon and fiber up to the blend of the heterophasic propylene polymer compsn of 20wt%, and said fiber has improved flexibility.
But, still there is demand for propene polymer with good spinning property, it can easily be woven into flexible fibre or long filament.Thus, the objective of the invention is, the prolylene polymer composition with good spinning property is provided, it can be converted into " soft feel " fiber and non-woven fabrics, keeps the well balanced of mechanical property simultaneously.
Thus, the invention provides a kind of prolylene polymer composition, it comprises (based on the summation of A+B):
(A) 55～95wt%, more preferably propylene copolymer or the propylene copolymer compositions of 70～90wt%; Contain up to 10wt%, be preferably 0.8～10wt%, the terminal olefin unit outside the propylene with 2～10 carbon atoms of 0.8～5wt% (based on propene polymer (A)) more preferably, the MFR of said propylene copolymer or propylene copolymer compositions (A) scope is 10～60g/10min, be preferably 15～35g/10min; With
(B) 5～55wt%, the prolylene polymer composition of 10～30wt% more preferably comprise (based on component (B)):
(a) 5～50wt%, be preferably 10～40wt%, more preferably the following xylene soluble part of 25 ℃ of 20～35wt% less than 20wt%, be preferably the alfon of 2～15wt%, or propylene and at least a has the multipolymer of the terminal olefin outside the propylene of 2～10 carbon atoms; Said multipolymer contains greater than the following xylene soluble part of the propylene units of 85wt% and 25 ℃ less than 20wt%;
(b) 0～20wt%, the ethene that is preferably 5～15wt% and at least a multipolymer with terminal olefin of 3～10 carbon atoms, said multipolymer at least partly are insoluble to YLENE under 25 ℃; With
(c) 40～95wt%, the propylene and at least a that is preferably 50～75wt% have the multipolymer of the terminal olefin outside the propylene of 2～10 carbon atoms, and said multipolymer contains terminal olefin unit less than 40wt%, be preferably under 20～38wt% and 25 ℃ and be partially soluble in YLENE at least.
This propylene copolymer or prolylene polymer composition (A) preferably have at least a performance in following group:
-fusing point is equal to or higher than 145 ℃;
-25 ℃ of following xylene soluble parts are less than 15wt%, more preferably less than 12wt%; With
-heterogeneity index (PI) value scope is 3～6, more preferably 2.5～4.5.
According to first kind of embodiment, this prolylene polymer composition (A) comprising:
(I) 20～80wt%, more preferably 30～70wt% alfon or have the propylene copolymer of the terminal olefin outside at least a propylene with 2～10 carbon atoms, said multipolymer contains up to 1.5wt%, is preferably the terminal olefin unit of 0.01～0.5wt%; With
(II) 20～80wt%, the propylene copolymer of 30～70wt% more preferably with the terminal olefin outside at least a propylene with 2～10 carbon atoms; Said multipolymer contains up to 10wt%, is preferably 0.8～10wt%, the terminal olefin unit of 0.8～5wt% more preferably; Prerequisite is that the terminal olefin total content of this prolylene polymer composition (A) is up to 10wt%.When the terminal olefin unit outside the propylene is ethene; The ethylene content difference is generally at least 0.8% unit between polymkeric substance (I) and the polymkeric substance (II); Be preferably 1% unit, 2% unit more preferably, and when the terminal olefin unit outside the propylene is the C4-C10 terminal olefin; Said difference is at least 1.5% unit, is preferably 2% unit.
According to another embodiment, this propylene polymerization composition copolymer or propylene copolymer compositions (A) are selected from:
(i) propylene copolymer or propylene copolymer compositions; The unit that contains 0.8wt% at least derived from the terminal olefin outside at least a propylene with 2～10 carbon atoms; The fusing point of said propylene copolymer or propylene copolymer compositions is equal to or higher than 155 ℃; Xylene soluble partly is lower than 5wt%, the intensification elution fractionation (TREF) through adopting YLENE under polymer moieties that 25 ℃～95 ℃ TR is collected and room temperature xylene soluble ratio partly greater than 8;
(ii) propylene copolymer or propylene copolymer compositions; Contain unit derived from the terminal olefin outside at least a propylene with 2～10 carbon atoms greater than 2.5wt%; The fusing point of said propylene copolymer or propylene copolymer compositions is equal to or higher than 153 ℃; Xylene soluble partly be lower than 10wt%, preferably be lower than 8wt% and through TREF under polymer moieties that 25 ℃～95 ℃ TR is collected and room temperature xylene soluble ratio partly greater than 4, be preferably greater than 4.5.
Preparation for propylene copolymer or prolylene polymer composition (A); In the presence of the terminal olefin outside at least a propylene with 2～10 carbon atoms with the propylene units polymerization; This terminal olefin is derived from ethylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene preferably, is preferably ethene especially.
According to first kind of embodiment, this propylene copolymer or prolylene polymer composition (A) can directly preparations at least one polymerization procedure in the presence of high Stereoselective out-phase Ziegler-Natta catalyst system.Alternatively and more preferably, precursor propylene copolymer that this propylene copolymer or prolylene polymer composition (A) can be through will having MFR (A1) or preceding precursor copolymer or precursor prolylene polymer composition (A1) carry out chemical degradation and prepare.
According to preferred implementation, this propylene copolymer or prolylene polymer composition (A) can obtain through the method that comprises the following steps:
(1) the monomer polymerization at least one polymerization procedure that in the presence of the stereospecific Ziegler-Natta catalyst system of height, will suit; Obtain precursor propylene copolymer or precursor prolylene polymer composition (A1) thus; Its MFR (A1) scope is 0.4～10g/10min, is preferably 0.9～5g/10min; With
(2) make said precursor propylene copolymer or precursor prolylene polymer composition (A1) carry out chemical degradation, obtain prolylene polymer composition (A) thus, its MFR (A) scope is 10～60g/10min, and wherein MFR (A)/MFR (A1) scope is 6～30.
The Ziegler-Natta catalyst that is applicable to this propylene copolymer of preparation or prolylene polymer composition (A) and precursor propylene copolymer or precursor prolylene polymer composition (A1) comprises ingredient of solid catalyst; This ingredient of solid catalyst comprises at least a titanium compound and at least a electronic donor compound capable (the interior body of giving) with at least one titanium-halogen bond, and the two is carried on the magnesium chloride.This Ziegler-Natta catalyst system further comprises as the organo-aluminium compound of necessary promotor and external electronic donor compound randomly.
Suitable catalyst system is described in European patent EP 45977, EP361494, EP728769, EP1272533 and the International Patent Application WO 00/63261.
Preferably; This ingredient of solid catalyst comprises Mg, Ti, halogen and electron donor(ED); This electron donor(ED) is selected from list with the aromatic dicarboxylic acid that is positioned at adjacent-COOH group-and two-value, wherein should-at least one R alkyl of COOR group contains 3～20 carbon atoms.Preferred especially electron donor(ED) is selected from 2; 3-naphthalic acid diisobutyl ester; N-propyl phthalate, di-n-butyl, diisobutyl ester, two n-pentyl esters, two-2-ethylhexyl, di-n-octyl, two peopentyl esters, the monobutyl of phthalic acid and diisobutyl ester, isobutyl-ethyl phthalate(DEP); The normal-butyl ethyl phthalate(DEP) is described in European patent EP 45977 and EP728769.
According to preferred method, this ingredient of solid catalyst can pass through formula Ti (OR)
N-yX
yTitanium compound (wherein, n is the valency of titanium, and y is the number between 1～n), preferred TiCl
4With derived from formula MgCl
2The magnesium chloride of pROH adducts (wherein, p is the number between 0.1～6, and is preferred 2～3.5, and R is the alkyl with 1～18 carbon atom) prepares.This adducts can be aptly through with pure and mild magnesium chloride with the immiscible unreactive hydrocarbons of this adducts in the presence of mix with sphere and make, the fusing point (100～130 ℃) of this adducts down agitation condition operate down.Subsequently, with the quick cancellation of emulsion, make adducts be frozen into the form of spheroidal particle thus.The case description of the spherical adduct that makes according to this operation is in US4, and 399,054 and US4,469,648.Can with thus obtained adducts directly with the reaction of Ti compound, the dealcoholization (80～130 ℃) that perhaps can it be carried out in advance thermal control, thus the wherein pure mole number of acquisition usually less than 3, be preferably 0.1～2.5 adducts.With the reaction of Ti compound can be through this adducts (dealcoholysis or itself) be suspended in cold TiCl
4Carry out in (common 0 ℃); Mixture heating up is elevated to 80～130 ℃ and remained under this temperature 0.5～2 hour.Can be with adopting TiCl
4Processing carry out 1 time or repeatedly.TiCl can adopted
4Processing during give body in adding, and can be with the processing repetition one or many that adopts electronic donor compound capable.Usually, formula (I) SUMATRIPTAN SUCCINATE is with respect to MgCl
2The use mol ratio be 0.01～1, be preferably 0.05～0.5.The preparation of spherical catalyst component for example is described among the European patent application EP-A-395083 and International Patent Application WO 98/44009.The surface-area (through the BET method) that the ingredient of solid catalyst that obtains according to aforesaid method shows is generally 20～500m
2/ g and be preferably 50～400m
2/ g, and overall porosity (through the BET method) is greater than 0.2cm
3/ g, be preferably 0.2～0.6cm
3/ g.Because radius is up to 10.000
Porosity (Hg method) usually scope be 0.3～1.5cm
3/ g, be preferably 0.45～1cm
3/ g.
Organo-aluminium compound is preferably alkyl-Al, is selected from trialkyl aluminium compound, like for example triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium.Also can use trialkylaluminium and aluminum alkyls muriate, alkyl aluminum hydride or alkylaluminium sesquichloride such as AlEt
2Cl and Al
2Et
3Cl
3Mixture.
Preferred external electronic donor compound comprises silicon compound, ester such as 4-ethoxy benzonitrile acetoacetic ester, heterogeneous ring compound and especially 2,2,6,6-tetramethyl piperidine and ketone.Another kind of preferred external donor compound is formula R
a 5R
b 6Si (OR
7)
cSilicon compound, wherein a and b are integer 0～2, c be integer 1～3 and (a+b+c) sum be 4; R5, R6 and R7 are alkyl, naphthenic base or the aryl with 1～18 carbon atom, randomly contain heteroatoms.Particularly preferably be methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane and 1; 1; 1-trifluoro propyl-2-ethyl piperidine base-dimethoxy silane and 1; 1,1-trifluoro propyl-metil-dimethoxy silane.The consumption of this external electronic donor compound makes that the mol ratio between organo-aluminium compound and the said electronic donor compound capable is 0.1～500.
This polymerization can be in liquid phase, in the gas phase or in liquid phase-gas phase, in continuous or batch reactor such as fluidized-bed or slurry-phase reactor, carry out.Preferably, said propylene copolymer or prolylene polymer composition (A) or said precursor propylene copolymer or precursor prolylene polymer composition (A1) can prepare through the gas-phase polymerization processes of at least two interconnected polymeric areas, carrying out.Said polymerization process is described in European patent EP 782587 and the International Patent Application WO 2/02929.In with propylene and at least a terminal olefin feeding first and second interconnected polymeric areas wherein, in the presence of catalyst system, carry out this process, and therefrom discharge the polymkeric substance that makes.Growing polymer particles flows through the first said polymeric area (riser tube) under condition of fast fluidization; Leave said first polymeric area and get into the second said polymeric area (downtake); They therefrom flow through with dense form under the effect of gravity; Leave said second polymeric area and be incorporated into said first polymeric area once more, set up two polymkeric substance circulations between the polymeric area thus.Usually, the condition of fast fluidized is through monomer gas mixture said first polymeric area of feeding under the point of the polymkeric substance of introducing growth is once more set up in first polymeric area.Transmission gas is higher than the transfer rate under the operational condition and is generally 2～15m/s to the speed of first polymeric area.In second polymeric area, wherein polymkeric substance flows with dense form under the effect of gravity, reaches the solid high intensity values, and it is near the loose density of polymkeric substance; Thus can streamwise obtain the positive effect of pressure, make that under the help that need not mechanical means, polymkeric substance being introduced first reaction zone once more becomes possibility.Like this, set up " loop " circulation, it limits through the calorific loss of the pressure equilibrium between two polymeric areas with this system of introducing.Randomly, in polymeric area, keep one or more rare gas elementes such as nitrogen or aliphatic hydrocarbon, consumption makes the dividing potential drop sum of rare gas element be preferably 5～80% of gas stagnation pressure.Operating parameters for example temperature is those that use always in the gas-phase olefin polymerization technology, for example between 50 ℃～120 ℃, is preferably 70 ℃～90 ℃.This method can be at 0.5～10MPa, be preferably under the working pressure of 1.5～6MPa and carry out.Preferably, various catalyst components are fed first polymeric area in the arbitrfary point of said first polymeric area.But they also can be in the feeding of the arbitrfary point of second polymeric area.In this polymerization technique, provide completely or partially to stop that the gas that exists in the riser tube and/or liquid mixture get into downtake and composition is different from the gas of the gaseous mixture in the riser tube and/or the equipment that liquid mixture is introduced downtake.According to preferred implementation, through one or more introducing pipelines said gas and/or liquid mixture that composition is different from the gaseous mixture in the riser tube are introduced downtake, a kind of mixture gets into downtake before having stoped effectively.Randomly, the gas that can difference that wait to feed downtake be formed and/or liquid mixture are with the form feeding of partially or completely liquefaction.Through advance in the reactor drum shown in the diagram in Fig. 4 of International Patent Application WO 00/02929 polymerization process and through independently with comonomer and conventional molecular weight regulator, particularly hydrogen in varing proportions metering feeding at least one polymeric area, particularly riser tube, can cut out MWD and the PI value thus of the polymkeric substance of growth expediently.
In the preferred method of this prolylene polymer composition of preparation (A); Can carry out chemical degradation step (2) through with precursor propylene copolymer or precursor prolylene polymer composition (A1) and sufficient quantity, preferred 0.001～0.20wt%, the more preferably radical initiator processing of the foundation technology well known in the art of 0.04～0.10wt%.Preferably, contact, carry out this chemical degradation through under shear conditions, polymer materials and at least a radical initiator being equal to or higher than under the temperature of decomposition temperature of radical initiator.Preferred radical initiator is 150 ℃～250 ℃ superoxide for the decomposition temperature scope; Like ditertiary butyl peroxide, dicumyl peroxide, 2; 5-dimethyl--2; 5-two (t-butylperoxy) hexin and 2,5-2 (selling with title Luperox 101 or Trigonox 101) by Akzo.
In the prolylene polymer composition (B); Partly (B) (a) and the propene polymer of B (c) be the multipolymer that propylene and at least a has the terminal olefin outside the propylene of 2～10 carbon atoms; Wherein preferred terminal olefin is selected from ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, is preferably ethene especially.B component (b) is ethene and at least a multipolymer with terminal olefin of 3～10 carbon atoms, and wherein preferred terminal olefin is selected from propylene and above-mentioned terminal olefin, is preferably propylene especially.Partly (B) (b) can randomly contain conjugation or non-conjugated diene with (B) (c), like divinyl, 1, and the own hexadiene of 4-, 1,5-hexadiene and ethylidene-norbornylene-1.When diene existed, content was 0.5～10wt% with respect to the weight of (b)+(c).
Total ethylene content preferable range of prolylene polymer composition (B) is 15～35wt%.
Partly (B) ethene/C3-C10 alpha-olefin copolymer solvability in 25 ℃ of following YLENE (b) is lower than 20wt%, and preferably is insoluble to YLENE under the room temperature.
Partly (B) propylene/C2-C10 alpha-olefin copolymer solvability in 25 ℃ of following YLENE (c) is greater than 50wt%, and more preferably it thoroughly is dissolved in YLENE under 25 ℃, and its intrinsic viscosity scope is 1.5～4.0dl/g, more preferably 1.7～3.0dl/g.
Prolylene polymer composition (B) can prepare through the sequential polymerization at least two stages; Wherein be right after polymer materials that ground formerly forms in the polyreaction in the presence of carry out each polymerization stage (except that the fs) subsequently; Wherein polymer moieties (B) (a) preferably prepares at least one fs, and multipolymer part (B) (b) prepares at least one subordinate phase with (B) (c).This polymerization stage can carry out in the presence of Ziegler-Natta catalyst and/or metallocene catalyst.Preferably; All polymerization stages carry out in the presence of the Ziegler-Natta catalyst that comprises ingredient of solid catalyst; This ingredient of solid catalyst comprises titanium compound and at least a electronic donor compound capable (the interior body of giving) with at least one titanium-halogen bond, and the two loads on the magnesium chloride.This Ziegler-Natta catalyst system further comprises as the organo-aluminium compound of necessary promotor and external electronic donor compound randomly.
Suitable catalyst system is described in European patent EP 45977, EP361494, EP728769, EP1272533 and the International Patent Application WO 00/63261.Prepare like preceding description identical with external donor, organo-aluminium compound and ingredient of solid catalyst in preferred.
This polymerization can be in liquid phase, in the gas phase or in liquid phase-gas phase, in continuous or batch reactor such as fluidized-bed or slurry-phase reactor, carry out.For example; Can in liquid phase, carry out (B) polymerization (a) of propene polymer part; Use liquid propene as thinner, in gas phase, carry out simultaneously copolymerization stage with obtain multipolymer part (B) (b) with (B) (c), except monomeric partly degassed, do not have the intermediate stage.Alternatively, can all sequences polymerization stage be carried out in gas phase.The polymerization temperature of each several part preparation can be identical or different and be generally 40 ℃～90 ℃.The common scope of polymerization pressure is 5～30 crust, if in gas phase, carry out the polymeric words.The case description of prolylene polymer composition (B) is in European patent EP 472946, International Patent Application WO 03/011962 and WO00/02929.
The melt flow preferable range of prolylene polymer composition (B) is 10～60g/10min, is preferably 15～35g/10min especially.Said prolylene polymer composition (B) can directly be obtained perhaps by foregoing polyreaction, alternatively makes melt flow (B1) carry out chemical degradation, particularly peroxo-less than the precursor prolylene polymer composition (B1) of MFR (B) and degrades and obtain.The chemical degradation of precursor prolylene polymer composition (B1) can carry out according to method as known in the art, as previously mentioned.
Prolylene polymer composition of the present invention may further include additive commonly used in the polyolefin field; Like oxidation inhibitor, photostabilizer, nucleator, antacid, tinting material, filler and modifier for processing, foundation method well known in the art is added to said additive in propylene copolymer or the prolylene polymer composition (A) and/or is added in the prolylene polymer composition (B) usually.
Prolylene polymer composition of the present invention can prepare according to currently known methods, like dried blend under shear conditions or through melt blending component (A) and (B).Preferably, the preparation component (A) and the blend of additive (B) and randomly obtain dried blend thus in the traditional mixer (for example, rotating cylinder-mixing machine).Alternatively, can with component simultaneously or respectively direct metering feeding to single-or two-screw extrusion press in, in identical or different section of this equipment.The common scope of extrusion temperature is 170～250 ℃.
Fiber or the long filament that comprises prolylene polymer composition of the present invention can adopt that commonly known technology and equipment prepare in this area, promptly through in being suitable for preparing the legacy equipment of single or conjugated fibre or long filament with this prolylene polymer composition melt-spinning.According to another embodiment, this conjugated fibre or long filament can have " cot structure "." fiber or long filament with cot structure " implication in this article is; Have axially extended interface and comprise at least two kinds of component fibers or long filament; Be at least one inner core and at least one crust, said at least two kinds of components comprise the different polymer material and link to each other along this axially extended interface.In core-skin fibre or long filament, skin thickness can be that the perhaps skin thickness of homogeneous can be inhomogenous around the circumference of fiber or filament cross.Said fiber or long filament with skin-core structure can adopt the traditional apparatus for melt spinning with concentric annular mould to prepare.Prolylene polymer composition of the present invention can be used to have the fiber of skin-core structure or the crust of long filament expediently.This inner core can comprise any polymer materials that is generally used for spunbond application, according to the final performance of the expectation of this conjugated fibre or long filament.Preferably, this core-skin fibre or long filament comprise 50～90wt%, more preferably polymer materials and 10～50wt%, the more preferably prolylene polymer composition of the present invention of the formation exodermis of 20～35wt% of the formation sandwich layer of 65～80wt%.Particularly advantageously be that core-skin fibre or long filament comprise the prolylene polymer composition of the present invention of formation exodermis of polymeric material section and 30wt% of the formation sandwich layer of 70wt%.
Prolylene polymer composition of the present invention shows splendid spinning property; Be that they can be spun into fiber or long filament with high spinning speed and do not rupture; And obtain simultaneously to give fiber or the long filament that improves flexibility, it keeps good mechanical properties, i.e. H.T. and high elongation at tear.Spinning speed implication in this article is the coiling speed of spinning machinery.Preferably, fiber of the present invention or long filament show one or more performances of following group:
-soft index is equal to or higher than 1000l/g, and more preferably scope is 1000～1200l/g;
-elongation at break scope is 150～200%;
-toughness is higher than 20cN/tex, more preferably is higher than 23cN/tex; With
-denier range is 0.8～8dtex, more preferably 1.0～4.0dtex.
Soft index is for estimating the flexible conventional measure of fiber.
Adopt prolylene polymer composition of the present invention; Can make expediently and have fiber or the long filament that improved toughness/snappiness balance and combination have excellent spinning property; Said fiber or long filament have skin-core structure; Wherein this cortex comprises prolylene polymer composition of the present invention, and sandwich layer comprise have low 25 ℃ of following xylene soluble parts, preferably be lower than 5.0wt%, more preferably less than 3wt% and high modulus in flexure, preferably be higher than 1100MPa, more preferably greater than the alfon of 1300MPa.The commercially available acquisition of said alfon.Preferably, the present invention has the fiber of skin-core structure or the cortex proportion scope of long filament is 20～40wt%, with respect to the gross weight of this long filament.
Fiber of the present invention or long filament can be converted into fabric.According to preferred implementation of the present invention, can this fiber be converted into non-woven fabrics, particularly spun-bonded non-woven fabrics.
Spunbond technology is attached to fiber sprinning and fibrous reticulum formation in the single manufacturing processed.When molten polymer leaves spinning nozzle, form fiber, from spinning nozzle, pull out long filament through the freezing air cancellation and through high-pressure air usually.Subsequently long filament being deposited on the motion that forms non-woven fabrics is with.Fabric weight is decided by the turnout of each spinneret hole, the number in hole and the speed of motion band.Subsequently, can fabric be bondd through different methods, like thermal caking, chemical bonding or needle punching, preferred thermal caking.Through thermal caking, with passing through between the calender roll that heats under the temperature of fabric in being generally comprised within 110 ℃～150 ℃ of scopes, preferred 120 ℃～130 ℃.Prolylene polymer composition of the present invention obtains to have the spun-bonded non-woven fabrics of excellent flexibility and good mechanical properties.The flexibility of non-woven fabrics is relevant with the rigidity of fabric and can represent through crooked soft index (BSI).BSI (according to hereinafter described method measurement) depends on the bending length of material, and it is measure (drape) of its draping property.Material is soft more, and bending length is low more.The BSI value of non-woven fabrics of the present invention is equal to or higher than 24l/mm.
Measure the performance of mentioning among this specification sheets and the embodiment according to following method.Given embodiment is used for setting forth and non-limiting the present invention.
The air inlet mol ratio: through gas chromatographic measurement
Comonomer (C2) content: through IR spectrum
Melt flow (MFR): according to ISO1133 (230 ℃ 2.16kg) are measured
Intrinsic viscosity: in 135 ℃ of following naphthanes, measure
Modulus in flexure: measure according to ISO178
Fusing point, melting enthalpy and Tc: through dsc measurement, temperature variation is 20 ℃/min
Heterogeneity index (PI)
Parallel-plate rheometer model RMS-800 through using RHEOMETRICS (USA) to sell measures under 200 ℃ of temperature, under the oscillation frequency that is increased to 100rad/sec from 0.1rad/sec, operates.From the modulus separation value, can draw PI through equality:
P.I.=54.6 * (modulus separation)
-1.76
Wherein, modulus is separated as is given a definition:
Frequency/G " frequency during=500Pa during modulus separation=G '=500Pa
Wherein, G ' is storage modulus and G " is out-of-phase modulus.
The xylene soluble part
2.5g polymkeric substance and the introducing of 250mL o-Xylol are equipped with in the glass flask of refrigerator and mechanical stirrer.Temperature was elevated to the boiling point of solvent in 30 minutes.Subsequently thus obtained solution was remained on the following also restir of backflow 30 minutes.Subsequently the flask of sealing was remained in the ice-water bath 30 minutes and the water bath with thermostatic control under 25 ℃ in 30 minutes.Thus obtained solid filtering filtration on paper fast and 100mL filtrating being poured in the aluminum container of previous weighing, is heated it on the hot-plate under the nitrogen gas stream, remove through evaporation thus and desolvate.Subsequently container is remained in 80 ℃ of stoves under the following vacuum up to obtaining constant weight.The weighing resistates is to confirm the per-cent of xylene soluble polymkeric substance.
The fiber number of long filament
From the long rove of 10cm, choose 50 fibers arbitrarily and weigh.The gross weight of these 50 fibers is represented with mg, multiply by 2, and obtaining thus with dtex is the fiber number of unit.
The toughness of long filament and elongation at break
From the 500m rove, cut out the long fragment of 100m and choose single fiber arbitrarily.Each single fiber is fixed on the clip of Instron Dynamometer (model 1122) and tension to fracture; Wherein pulling speed is 20mm/min for the elongation that is lower than 100% and is 50mm/min for the elongation greater than 100%, and the initial distance between the clip is 20mm.Processing measuring limit intensity (breaking load) and elongation at break on (MD) and opposite (TD) direction simultaneously.Calculate toughness through following equality:
Toughness=US (cN) * 10/ fiber number (dtex)
Flexibility on the fiber
Measure the soft index of fiber through this method.Soft Index for Calculation is the weight (l/g) of a bundle fiber, under standard conditions, measures its length.The fibrous bundle of preparation about 400dtex of linear density and length 0.6m.The end of this bundle is fixed on the clip of twisted metering facility (Torcimetro Negri e Bossi SpA) and applies left twisted 102 times.Twisted bundle is taken off from this equipment carefully, avoid any backtwisting.The two ends of twisted bundle are connected and twine around the ground doubling each other, taken a fancy to up to this bundle and resemble rope.For 3 samples of each test preparation.This beam bending is fixed between the roller of Clark flexibility tester in two and with end, and the distance of protecting between the special two halves is 1cm.This equipment is stopped to right rotation and when this bundle makes its bending direction reverse, write down angle of rotation (a).Subsequently, should restraint to anticlockwise and make its curved side reverse, write down angle of rotation (b) up to it.The height of regulating two these bundles on the roller subsequently equals 90 ° and adopt the said height of suitable device measuring (h) of sensitivity 1mm to (a)+(b) sum.Among these two angle a and the b each should be no more than 45 ° ± 15 ° of limits.With the height (h) that takes off and cut on this bundle slave unit corresponding to previous observed value.Through the analytical balance of tolerance range 0.1mg this chopped beam of weighing.By the soft index of computes:
S.I.＝(1/w)*100
Wherein, w for this chopped beam be the weight of unit with g.On average provide the result based on 3 samples.
Crooked soft exponential is measured on the non-woven fabrics
Once make the long and wide sample of 50mm of 200m with single-layer nonwoven is folding, and be placed on the smooth box with following size: highly=35mm, length=300mm, width=100mm.This sample is slowly promoted along its surface to arrive its underlying surface (referring to Fig. 1) thus up to its bending.Distance between box surface and the touch down point is bending length (bl), is unit representation with mm.The end value of bending length is the MV based on 10 samples.Calculate this BSI by following equality:
B.S.I.＝(1/bl)*1000
Wherein, bl is the bending length of nonwoven sample, is unit with mm.
The flexibility of panel test
Please 20 optional people touches and estimates the softness of sample, through contrasting with control sample (being generally used for the alfon of fiber).As follows sample is graded: 1=is lower than control samples; 2=equals control samples; 3=is superior to control samples; 4=is superior to control samples greatly; 5=is splendid.Numeral is corresponding to average rank in the table.
The preparation of propene polymer (A)
According to embodiment the 5, the 48th～55 row of European patent EP 728769, preparation is used to prepare the solid catalyst of precursor propylene copolymer or precursor prolylene polymer composition (A1), and difference only is to add 200mLTiCl
4Subsequently with normal heptane washing repetition four times.Use triethyl aluminum (TEAL) as promotor and dicyclopentyl dimethoxyl silane as external donor.Propene polymer (A1) prepares in a single polymerization procedure, through monomer and catalyst system feeding are comprised in the Gas-phase reactor of two interconnected polymeric areas, riser tube and downtakes, described in International Patent Application WO 00/02929.The comonomer of specified amount is only fed first polymeric area (riser tube); Distinguish two gas compositions in the polymeric area through the mode of barrier charging.The polymer beads that obtains is carried out VT to remove unreacted monomer and dry.Propene polymer (A1) is extruded in the presence of 0.030wt% calcium stearate, 0.19wt%
B501W (Ciba Specialty Chemicals sale) and 0.073wt%
101 (superoxide that Akzo sells), made prolylene polymer composition (A).Reported polymerizing condition in the table 1 and adopted before the superoxide chemical degradation and the performance of propene polymer afterwards.
Table 1
Embodiment 1～3 and comparative example 1c～2c
Through in legacy equipment, doing blend; The aforesaid propylene polymkeric substance (A) of the different weight percentage of forming shown in making below having and the blend of component (B); And spinning in Leonard 25 spinning guiding pipeline subsequently, wherein screw rod L/D ratio is 25, screw diameter is that 25mm and compression ratio are 1: 3.This pipeline is sold by Costruzioni Meccaniche Leonard-Sumirago (VA).Reported the performance of blend composition, operation spinning condition and the long filament that obtains in the table 2.
Component (B) is a prolylene polymer composition, comprises (based on the per-cent of whole component (B)):
(a) propylene/ethylene copolymer of 33wt% contains the units derived from ethylene (with respect to part (a)) of 4.3wt%, and the xylene soluble that has is partly for 9wt%;
(b) ethylene/propene copolymer of 6wt% contains the units derived from ethylene (with respect to part (b)) of 94wt%, and is insoluble to YLENE fully; With
(c) propylene/ethylene copolymer of 61wt% contains the units derived from ethylene (with respect to part (c)) of 30wt%, and can be dissolved in YLENE fully.
The MFR of component (B) is 27g/10min.
Table 2
The spinning property of the clear prolylene polymer composition of the present invention of maximum spinning Speedometer Drive.This value is corresponding to the high spinning speed that can keep 30 minutes and not have filament breakage.Prolylene polymer composition of the present invention has splendid spinning property, and is suitable with propene polymer (A) (referring to comparative example 1) at least, and can process and have the long filament that excellent flexibility keeps H.T. and high elongation at tear simultaneously.The consumption that increases component (B) is higher than desired scope, and the flexibility of spinning property and/or long filament is not brought obvious improvement, but influences the mechanical property of long filament unfriendly on the contrary.
Comparative example 3c and 4c
MFR through preparation different weight percentage in above-mentioned identical equipment is the blend of the component (B) used among alfon (being sold with title Moplen HP561R by Basell) and the embodiment 1 of 25g/10min, and is spun into long filament under the condition of in table 2, reporting.Reported the performance of blend composition, maximum spinning speed and long filament in the table 3.
Table 3
Embodiment 4～5 and comparative example 5c
The prolylene polymer composition of embodiment 1,3 and comparative example 1c is processed on spunbond circuit, made the non-woven fabrics of embodiment 4,5 and comparative example 6c thus respectively.The operational condition of spunbond circuit and the performance of non-woven fabrics have been reported in the table 4.
Table 4
Show higher flexibility and the fabric toughness that equates according to non-woven fabrics of the present invention, if when comparing with the non-woven fabrics that obtains by prolylene polymer composition (A).
Embodiment 6 and 7
The Moplen HP561R that adopts Basell as sandwich layer and according to prolylene polymer composition of the present invention as cortex, make the core-skin long filament.Prolylene polymer composition of the present invention comprises the aforesaid propylene polymkeric substance (A) and the blend (B) of different weight percentage, and preparation as described in the embodiment 1.This core-skin long filament contain 70wt% sandwich layer and 30wt% cortex and be applicable to that preparation has on the legacy equipment of mould of skin-core structure and prepare being equipped with.This core-skin long filament is processed to make non-woven fabrics on the conventional spunbond circuit.Cortex composition, the operational condition of spunbond circuit and the performance of non-woven fabrics have been reported in the table 5.
Table 5
Claims (8)
1. prolylene polymer composition comprises the summation based on A+B:
(A) propylene copolymer of 55～95wt% or propylene copolymer compositions; Contain based on the terminal olefin unit outside the propylene of propene polymer A 0.8 to 10wt% with 2～10 carbon atoms; The MFR of said propylene copolymer or propylene copolymer compositions (A) scope is 10～60g/10min; Fusing point is equal to or higher than 145 ℃, and 25 ℃ of following xylene soluble parts are 2.5～6 less than 15wt% and heterogeneity index PI value scope; With
(B) prolylene polymer composition of 5～55wt% comprises based on B component:
(a) 25 of 5～50wt% ℃ of following xylene soluble parts are less than the alfon of 20wt%, or propylene and at least a has the multipolymer of the terminal olefin outside the propylene of 2～10 carbon atoms; Said multipolymer contains greater than the following xylene soluble part of the propylene units of 85wt% and 25 ℃ less than 20wt%;
(b) ethene of 0～20wt% and at least a multipolymer with terminal olefin of 3～10 carbon atoms, said multipolymer at least partly are insoluble to YLENE under 25 ℃; With
(c) propylene of 40～95wt% and at least a has the multipolymer of the terminal olefin outside the propylene of 2～10 carbon atoms; Said multipolymer contains that the solubleness in YLENE is higher than 50wt% under terminal olefin unit and 25 ℃ of 20-38wt%, and its intrinsic viscosity scope is 1.5-4.0dl/g;
Wherein component (A) and weight percentage sum (B) equal 100%.
2. the prolylene polymer composition of claim 1, wherein component (A) is a prolylene polymer composition, it comprises:
(I) alfon of 20～80wt% or have the propylene copolymer of the terminal olefin outside at least a propylene with 2～10 carbon atoms, said multipolymer contains the terminal olefin unit up to 1.5wt%; With
(II) the propylene copolymer of 20～80wt% with the terminal olefin outside at least a propylene with 2～10 carbon atoms, said multipolymer contains the terminal olefin unit up to 10wt%,
Prerequisite is that the terminal olefin total content of this prolylene polymer composition (A) is 0.8-10wt%.
3. the fiber or the long filament that comprise the prolylene polymer composition of claim 1 or 2.
4. the spunbond non-woven fabrics that comprises the prolylene polymer composition of claim 1 or 2.
5. the spunbond non-woven fabrics of claim 4, the crooked soft index that it has is equal to or greater than 24l/mm.
6. have the fiber or the long filament of skin-core structure, wherein this cortex comprises the prolylene polymer composition of claim 1 or 2, and sandwich layer comprises that 25 ℃ of following xylene soluble parts are less than 5.0wt% and the modulus in flexure alfon greater than 1100MPa.
7. prepare the method for fiber or long filament, it is characterized in that, it comprises the step with the prolylene polymer composition melt-spinning of claim 1 or 2.
8. prepare the method for spunbond non-woven fabrics, it is characterized in that, it comprises that spunbond comprises fiber or the step of long filament of the prolylene polymer composition of claim 1 or 2.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05112518 | 2005-12-20 | ||
| EP05112518.5 | 2005-12-20 | ||
| US75327305P | 2005-12-22 | 2005-12-22 | |
| US60/753,273 | 2005-12-22 | ||
| PCT/EP2006/068225 WO2007071496A1 (en) | 2005-12-20 | 2006-11-08 | Soft non-woven fabrics |
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| Publication Number | Publication Date |
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| CN101341177A CN101341177A (en) | 2009-01-07 |
| CN101341177B true CN101341177B (en) | 2012-08-08 |
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| CN2006800483890A Expired - Fee Related CN101341177B (en) | 2005-12-20 | 2006-11-08 | Soft non-woven fabrics |
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| AT (1) | ATE513860T1 (en) |
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| CN104583302B (en) * | 2012-06-27 | 2017-06-06 | 道达尔研究技术弗吕公司 | For high-tenacity fiber and the Noblen of non-woven fleece |
| WO2015178423A1 (en) * | 2014-05-20 | 2015-11-26 | 三井化学株式会社 | Non-woven fabric laminate, and sanitary supplies |
| CN104928797A (en) * | 2015-06-10 | 2015-09-23 | 中国化学纤维工业协会 | Composite polyolefin fiber and preparation method thereof |
| WO2018167304A1 (en) * | 2017-03-17 | 2018-09-20 | Beaulieu International Group Nv | Polypropylene composition with improved tensile properties, fibers and nonwoven structures |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0632147A2 (en) * | 1993-06-17 | 1995-01-04 | Montell North America Inc. | Fibers suitable for the production of nonwoven fabrics having improved strength and softness characteristics |
| CN1685093A (en) * | 2002-09-25 | 2005-10-19 | 巴塞尔聚烯烃意大利有限公司 | Polypropylene fibres suitable for spunbonded non-woven fabrics |
-
2006
- 2006-11-08 AT AT06829955T patent/ATE513860T1/en not_active IP Right Cessation
- 2006-11-08 CN CN2006800483890A patent/CN101341177B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0632147A2 (en) * | 1993-06-17 | 1995-01-04 | Montell North America Inc. | Fibers suitable for the production of nonwoven fabrics having improved strength and softness characteristics |
| CN1685093A (en) * | 2002-09-25 | 2005-10-19 | 巴塞尔聚烯烃意大利有限公司 | Polypropylene fibres suitable for spunbonded non-woven fabrics |
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| ATE513860T1 (en) | 2011-07-15 |
| CN101341177A (en) | 2009-01-07 |
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