CN104350188A - Thermoplastic fibres with reduced surface tension - Google Patents

Abstract

The present invention relates to a method for producing thermoplastic fibres with reduced surface tension and to products to be produced from such thermoplastic fibres with reduced surface tension according to the melt-spinning method, wherein the thermoplastic to be used is mixed with a copolymer made of at least one alpha-olefin and at least one acrylic acid ester or methacrylic acid ester of an aliphatic alcohol.

Description

There is the capillary thermoplastic fiber of reduction

The present invention relates to a kind of for the production of have reduction capillary thermoplastic fiber method and relate to the obtainable product of capillary thermoplastic fiber from these by melt-spinning process with reduction, wherein make this have thermoplastic to be used to mix with a kind of copolymer, this copolymer is the acrylate of at least one alpha-olefin and at least one fatty alcohol (preferred 2-Ethylhexyl Alcohol) or the copolymer of methacrylate.

The product obtained by the thermoplastic fiber from polyamide or polyester race in implication of the present invention is fibrous nonwoven webs, nonwoven, weaven goods, line, yarn, rope, felt, stretch ring knitted fabric, non-crimped fabric or forming ring knitted fabric.Fibrous nonwoven webs or nonwoven are preferred products in implication of the present invention.A kind of fibrous nonwoven webs is fibrous by the loosely polymerization needing to combine.The intensity of fibrous nonwoven webs is only based on the adhesiveness that fiber is intrinsic.But, the impact that the latter may be processed.In order to process and use this fibrous nonwoven webs, it needs by consolidation, can use multiple method to this.Only the fibrous nonwoven webs of consolidation should be called a kind of nonwoven.In spoken language, do not carry out this distinguish.

Nonwoven is fundamentally different from weaven goods, stretch ring knitted fabric, non-crimped fabric and forming ring knitted fabric, and their feature is arrange independent fiber or line in a kind of mode determined by production technology.By contrast, nonwoven by its location only can by statistic law describe fibrous.

Fiber in a kind of nonwoven arranges each other randomly.Except other things, according to fibrous material (polymer such as, when artificial fibre), mull technique, fiber type (staple fiber or continuously filament fiber), fibre fineness and fibre orientation, nonwoven is classified.These fibers may be placed on a preferential direction in a kind of mode of restriction, or they may state in a kind of completely random orientation, as when the nonwoven of random arrangement.

When these fibers do not have preferential direction in their directrix (orientation), relate to a kind of isotropic nonwoven.When these fibers are in one direction than when frequently placing in the other direction, this is called anisotropy.

Therefore, nonwoven is textiles, and wherein fabric formation is not woven, forming ring is knitting, stretch ring is knitting or the layout of restriction affects, but by adjoint these fibre interferes of placement fixing subsequently.The fabric knitting with weaven goods and draw ring is compared, due to its use on multifunctionality and its lower manufacturing cost, nonwoven continues to enjoy annual growth.

The advantage of nonwoven is high specific area, and these production technologies allow the change of huge range on density, fiber size, pore size or thickness, and cause the substantial degree of isotropy in cloth.These favourable performances allow the many possible application in following item: medically for health product, surgical drape, coverlet, wound covering thing, gauze etc. particularly, be used as the rag of any type in the family and be used as bunting, tablecloth, napkin particularly, lining cloth is used as in clothing industry, for specialized application, particularly felt pad, cover pad or as the filter medium in engine/motor vehicles industry (such as oil filter) or as the barrier film (WO 2009/103537 A1) in battery.

Surface tension is for manyly serving decisive action in these application, because the surface tension reduced can cause such as ever-increasingly refusing water behavior, and this not only can play an important role for the application in the application in clothing industry but also the filter medium in motor vehicles industry.

The one that the production of spunbonded non-woven is included between spinning process and formation of fabrics technique directly combines.Not only melt-spinning process and dry spinning process but also wet spinning process are applicable to the formation of fabrics based on continuous filament fiber.Multiple fibre-forming polymer is called as a kind of parent material for nonwoven.Of the present invention is such as be made up as so-called melt-blown non-woven thing by melt-spun of the thermoplastic polymer from polyamide or polyester race based on continuous print nonwoven.Such as in EP 0 880 988 A1 or EP 1 473 070 A1, this melt-spinning process is described for polyester.Polyester nonwoven thing is described in EP 2 090 682 A1 or EP 2 092 921 A1.The polyester nonwoven thing produced by this melt-blown process is used to define a part for the theme of EP 0 466 381 B1 as a kind of filter medium.

Although due to the hydrophobic property (even when not having auxiliary agent) that polyolefin is intrinsic, the thermoplastic fiber's (such as polypropylene or polyethylene fiber) formed by polyolefin has relatively low surface tension, but the thermoplastic of higher surface tension and relative more polarity, preferably polyamide is relevant with polyester.Wherein this causes numerous application of problem in existence, although because need low surface tension, must use the polymer such as polyamide or polyester of relatively high value, such as, due to heat resistance not enough with regard to polyolefin or chemical resistance.This often condenses into a hope, the i.e. thermoplastic of even relative more polarity, as polyamide and polyester, can be modified to realizing lower capillary effect, retain familiar advantage, such as, as heat resistance, mechanical robustness and to oil and the chemical resistance of engine fuel simultaneously.

Use polyester as an example about breaking strength, describe in DE 19 937 729 A1 and need the characteristic of the thermoplastic fiber be spun into by being added with the thermoplastic impact being ready to use in it.In that, additive a kind ofly comprises acrylate among other things or the methacrylate copolyesters as monomeric unit.WO 2005/040257 A1 pursues a similar object, in polyester film, band and melting spinning fibre, namely uses ethylene alkyl acrylate copolymer with the mechanical property improving them such as tension stress intensity.Wherein add as preferably listing the copolymer being greater than 5%.

FR-OS 239 746 and US 3,378,609 describes oleophobic by a kind of aqueous emulsion of fluorinated polymer being applied to the weaven goods produced and the hydrophobic weaven goods based on polyester.EP 0 196 759 A1 describes the hydrophobic polyester fiber by giving polyester fiber polyoxyalkylene glycol and the uniqueness based on the water oil protective agent (not having with the essence of this polyester reactive) of fluorine subsequently.

Except other things, WO 2009/152349 A1 describes the health cloth using the fluorochemical based on fluoridized alkyl group (have and be up to four carbon atom) to modify as protective agent additive.The copolymer of this type of fluoridized material and acrylate or methacrylate enumerates by way of example.JP 2,003 193331 A describes the rubber reinforcement monofilament polyester using the copolymer of ethene and glycidyl methacrylate to modify except other things.

WO 2005/087868 A1 discloses ethylene copolymer-modified polyamide product, its can be obtained by this melt-spinning process and the fiber using e/x/y copolymer to modify, wherein E represents ethene, and X represents alkyl acrylate and Y represents glycidyl acrylate, glycidyl methacrylate or glycidyl vinyl ether except other things except other things.

WO 2008/083820 A1 finally discloses the soft yarn based on polyamide or polyester, and it can use the softening agent of ethylene alkyl acrylate polymer-modified.List methyl acrylate, ETHYL CYANOACRYLATE and butyl acrylate.

These prior art solutions all have following shortcoming, namely cause the surface tension of grease proofing and waterproof behavior change in each case only subsequently in an additional procedure of processing by auxiliary agent being applied to the realization of this weaven goods.Surface subsequently applies the processed complex degree level not only causing raising, and cause raising auxiliary agent desorption or by the risk washed off, this not only weakens desired skin effect but also may be associated with debatable environmental pollution, the not purifying (impurification) of such as, filtrate in the filter medium situation of post processing.Also be often necessary to rely on the chemicals fluoridized, these chemicals also need special consideration except very expensive, such as, about relating to by burning its genotoxic potential reclaimed.

Therefore the problem that the present invention addresses shifts to an earlier date modified polyamide/polyester, make capillary reduction be even possible under the product not having post processing to be produced by discussed thermoplastic fiber like this, and can realize under low-down materials'use.This modification should avoid the chemicals fluoridized further, is neutral color and is such, and namely processbearing astrocyte itself is not unacceptably damaged.Should be so further for reducing this capillary modification, namely they can be restricted to by the validity of the auxiliary agent added one does not have decisive influence (if yes) consumption to melt-spinning process.The fiber of acquisition like this should be differently can be processed into product further in that state, is processed into capillary fibrous nonwoven webs, nonwoven, weaven goods, stretch ring knitted fabric, non-crimped fabric or the forming ring knitted fabric with reduction especially.

It is a kind of for reducing based on the fiber of thermoplastic or the capillary method of filament for solving the scheme of this problem and theme of the present invention, it is characterized in that this thermoplastic is added with at least one alpha-olefin and does not replace fatty alcohol (preferably unsubstituted, the fatty alcohol with 6-30 carbon atom, more preferably 2-Ethylhexyl Alcohol) methacrylate or the E/X copolymer of acrylate, and this mixture to be spun into preferably by melt-spinning process subsequently.

Unexpectedly, find that this thermoplastic polyamide or polyester are added with has E/X copolymer to be used to be very effective in the surface tension reducing corresponding thermoplastic fiber and their derivative products according to the present invention, and therefore cause such as these based on the fiber of thermoplastic, preferred polyamide/polyester fiber, and the waterproof of their derivative products is modified.This has copolymer to be used to be so effective so that achieve capillary substance reduction even at very low concentrations according to the present invention, therefore there is not the decisive influence (if any) to this melt-spun.

The method preferably uses the mixture for spinning, and these mixtures are at least one thermoplastics of based on 99.9 to 10 weight portions, preferably 99.5 to 40 weight portions and more preferably 99.0 to 55 weight portions, and

0.1 to 20 weight portion, preferably 0.25 to 15 weight portion, more preferably 0.5 to 10 weight portion, also more preferably 0.75 to 6 weight portion, the E/X copolymer of the most preferably above-mentioned restriction of 1.0wt% to 2.0wt% particularly.

For being used as based on the fiber of thermoplastic, the fiber that preferential is based on the thermoplastic polymer from polyamide or polyester race.

For the fiber based on thermoplastic be used as from polyamide race, particularly preferably be the fiber based on fatty polyamide.

For the fiber based on thermoplastic being used as autopolyester race, particularly preferably be the fiber based on polyalkylene terephthalates.

Can obtain in many ways according to the thermoplastic polyamide that the present invention needs to be spun into and be synthesized by very different construction units.In concrete application scenarios, they are used individually or with processing aid, stabilizing agent, polymer-alloying gametophyte, especially elastomer-bonded.It is suitable that there is the blend (preferably having the blend of polyethylene, polypropylene or ABS) of other polymer a certain proportion of in addition, can optionally use one or more bulking agents in this case.The characteristic of polyamide can be improved, such as, about the breaking strength of such as particularly low-viscosity polyamides by mixed elastomer.The diversity that may combine provides very a large amount of products with very diverse nature.

Polyamide obtains by a large amount of existing program, these programs, depend on desired final products, relate to and use different monomeric building blocks, different chain-transferring agents carrys out realize target molecular weight also or have the post processing of monomer for expecting subsequently of reactive group.

The method of being correlated with for the production of the industry of polyamide is carried out frequently by the polycondensation under melt state.

In this context, polycondensation also comprises the hydrolytic-polymeric reaction of lactam.

Preferably polyamide-based (PA) is from Diamines and dicarboxylic acids and/or has the polyamide-based of the lactams of at least 5 ring memberses or the amino acids obtainable part crystalloid of correspondence.

Possible parent material comprises aliphatic and/or aromatic dicarboxylic acid class (such as adipic acid, 2, 2, 4-trimethyladipic acid, 2, 4, 4-trimethyladipic acid, azelaic acid, decanedioic acid, M-phthalic acid, terephthalic acid (TPA)), aliphatic and/or aromatic diamines are (such as tetra-methylenedimine, hexamethylene diamine, 1, 9-nonamethylene diamine, 2, 2, 4-trimethylhexamethylenediamine, 2, 4, 4-trimethylhexamethylenediamine), isomeric diamino-dicyclohexyl methane class, diaminocyclohexyl propane class, two aminomethyl cyclohexane, phenylenediamine, xylylene diamine class, aminocarboxylic acids (such as aminocaproic acid), and corresponding lactams.Comprise two or more copolyamide of described monomer.

Particularly preferably be use caprolactam and very particularly preferably be use epsilon-caprolactams.

Being particularly suitable for property extends to most of mold compound further, these mold compounds based on nylon-6, nylon-6,6 and other aliphatic or/and aromatic polyamide/copolyamide and each polyamide group on this polymer chain has 3 to 11 methylene groups.

According to the present invention obtain these polyamide and can also be used in the mixture of other polyamide-based and/or other polymer.

These polyamide can comprise conventional additives such as the mixture of releasing agent, stabilizing agent and/or flowing assistant.

The thermoplastic polyester needing to be spun into according to the present invention particularly preferably is the polyester of partially aromatic.

The polyester particularly preferably needing to be spun into is selected from the group of the derivative of polyalkylene terephthalates.The polyester very particularly preferably needing to be spun into is selected from the group of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate, also more preferably polybutylene terephthalate and polyethylene terephthalate, most preferably polybutylene terephthalate, or the mixture of these terephthalate.

The polyester of partially aromatic is the material comprising aliphatic portion and aryl moieties.

For the purposes of the present invention, polyalkylene terephthalates is the product of the mixture of aromatic dicarboxylic acid class or their reactive derivatives class (especially dimethyl esters class or anhydrides) and aliphatic, alicyclic or fragrant fat subsitutes race glycol and these reactants.

Preferred polyalkylene terephthalates is by terephthalic acid (TPA) (or its reactive derivatives) and have the aliphatic of 2 to 10 carbon atoms or alicyclic diol by known method (Plastics Handbook, VIII rolls up, 695FF page, Ka Er-sweat pool-Springer Verlag, Munich (Kunststoff-Handbuch, vol.VIII, p.695FF, Karl-Hanser-Verlag, Munich) 1973) obtainable.

Preferred polyalkylene terephthalates class contains the terephthalic acid (TPA) group based at least 80mol% of dicarboxylic acids, preferably 90mol%, and based at least 80mol% of diol component, the ethylene glycol and/or 1 of preferred at least 90mol%, ammediol and/or BDO group.

Preferred polyalkylene terephthalates class, except terephthalic acid (TPA) group, there are other aromatic dicarboxylic acid class groups of 8 to 14 carbon atoms or there is the aliphatic dicarboxylic acid class group of 4 to 12 carbon atoms up to 20mol% can be comprised, O-phthalic acid groups, isophthalic acid groups, naphthalene-2 particularly, 6-dicarboxylic acids group, 4,4 '-diphenyl dicarboxylic acid group, succinic acid group, adipic acid group, decanedioic acid group, azelaic acid group, cyclohexanediacetic group, cyclohexane dicarboxylic acid group.

Preferred polyalkylene terephthalates class, except ethene/1, ammediol/1, outside 4-butanediol glycol group, there are other aliphatic diol classes of 3 to 12 carbon atoms or there is the alicyclic diol class of 6 to 21 carbon atoms up to 20mol% can be comprised, 1,3-PD group specifically, 2-ethyl-1,3-PD group, neopentyl glycol group, 1,5-PD group, 1,6-hexylene glycol group, 1,4-CHDM group, 3-methyl-2,4-pentanediol group, 2-methyl-2,4-pentanediol group, 2,2,4-trimethyl-1,3-pentanediol group, 2,2,4-trimethyl-1,6-pentanediol group, 2-ethyl-1,3-hexylene glycol group, 2,2-diethyl-1,3-PD group, 2,5-hexylene glycol group, Isosorbide-5-Nitrae-two (β-hydroxy ethoxy) phenyl group, two (4-hydroxy-cyclohexyl) the propane group of 2,2-, 2,4-dihydroxy-1,1,3,3-tetramethyl-ring butane group, 2, two (3-beta-hydroxy ethoxyl phenenyl) the propane group or 2 of 2-, two (4-hydroxy propyloxy group phenyl) propane group (the DE A 25 07 674 (=US 4 035 958) of 2-, DE-A 25 07 776, DE-A 27 15 932 (=US 4 176 224)).

Can by conjunction with 3-or 4-unit's alcohol of relatively small amount or 3-or 4-unit carboxylic acid branching polyalkylene terephthalates class, likely to describe in DE-A 19 00 270 (=US-A 3 692 744).The example of preferred branching agent is trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane and pentaerythrite.

Worthless is use the branching agent more than 1mol% based on this acid constituents.

Particularly preferably be only from terephthalic acid (TPA) and reactive derivatives thereof (particularly its dialkyl esters) and ethylene glycol and/or 1, ammediol and/or 1, the polyalkylene terephthalates class that 4-butanediol is formed, particularly preferably is the mixture of polyethylene terephthalate and polybutylene terephthalate and these polyalkylene terephthalates classes.

Preferred polyalkylene terephthalates comprises further by least two kinds of above-mentioned acid constituents and/or the copolyesters class that formed by least two kinds of above-mentioned alkoxide components, and particularly preferred copolyesters is poly-(ethylene glycol/BDO) terephthalate.

Polyalkylene terephthalates has about 0.3dl/g to 1.5cm usually ³the inherent viscosity of/g, preferably 0.4dl/g to 1.3dl/g, more preferably 0.5dl/g to 1.0dl/g, allly all measures at 25 DEG C in 1:1 (w/w) phenol/o-dichloro-benzenes.

Can also be used in other polyesters and/or with the mixture of other polymer according to these thermoplastic polyester that the present invention is preferably spun into.Very particularly preferably be use polyethylene terephthalate (PET), polytrimethylene terephthalate or polybutylene terephthalate (PBT) or their mixture, particularly polybutylene terephthalate.

From consumption, polyester that the is rear or recovery of salvage material before consuming also can be used alone or as a mixture further, the preferred polyester reclaiming material from bottle in this case, so-called PET copolyesters.An one example looks like PET from the PET Kunststoffrecycling GmbH company of German Bei Sailixi-upper Di Fenba (Beselich-Obertiefenbach).

For the polyester be used as in melt-spun, particularly preferably be and comprise up to other dicarboxylic acids of 15mol% and/or dihydroxylic alcohols, particularly M-phthalic acid, adipic acid, diethylene glycol, polyethylene glycol, 1,4-CHDM, or other C _2-4poly-(the C of any one of aklylene glycol _2-4alkylidene) terephthalate.The polyethylene terephthalate preferably with the inherent viscosity (I.V.) in the scope from 0.5dl/g to 1.4dl/g, the polytrimethylene terephthalate with the I.V. of 0.7dl/g to 1.6dl/g or there is the polybutylene terephthalate of I.V. of 0.5dl/g to 1.8dl/g, and particularly preferably there is the polyethylene terephthalate of the inherent viscosity (I.V.) from 0.6dl/g to 1.0dl/g in scope or there is the polybutylene terephthalate of I.V. of 0.6dl/g to 0.9dl/g.

In order to reduce their surface tension, the thermoplastic needing to be spun into according to the present invention comprises the E/X copolymer of E at least one alpha-olefin and the unsubstituted fatty alcohol methacrylate of X mono-kind or acrylate.For being used as the component E of these copolymers, preferred alpha-olefin preferably has the carbon atom between 2 and 10 and can be unsubstituted or replaced by one or more aliphatic, alicyclic or aromatic group.Preferred alpha-olefin is selected from the group comprising following item: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 3-Methyl-1-pentene.Particularly preferred alpha-olefines is ethene and propylene, and ethene is very particularly preferred.The mixture of described alpha-olefin is also suitable.

The alpha-olefin content of this E/X copolymer is between 50wt% and 90wt%, preferably between 55wt% and 75wt%.

This E/X copolymer limits further by the second component except this alpha-olefin.What be suitable as this second component is alkyl esters or the aralkyl ester class of acrylic or methacrylic acid, its alkyl or aromatic alkyl group are formed by from 5-30 carbon atom, and only comprise the reactive functional groups (if yes) of least concentration, these reactive functional groups are selected from lower group, and this group comprises: epoxides, oxetanes class, anhydrides, acid imide, aziridines, furans, acids, amine.This alkyl or aromatic alkyl group can be straight or brancheds, and comprise alicyclic or aromatic group, replace simultaneously or by one or more ether or thioether functional group.In this context, the methacrylate be applicable to or acrylate also comprise from those of a kind of alkoxide component synthesis based on oligoethylene glycol or low polypropylene glycol (only having a hydroxyl and no more than 30 carbon atoms).

The alkyl of methacrylate or acrylate or aromatic alkyl group are preferably selected from the group comprising following item: 1-hexyl, 2-hexyl, 3-hexyl, 1-heptyl, 3-heptyl, 1-octyl group, 1-(2-ethyl) hexyl, 1-nonyl, 1-decyl, 1-dodecyl, 1-lauryl or 1-octadecyl.Particularly preferably be and there is 6-20 carbon atom, more preferably the unsubstituted alkyl of 8-20 carbon atom or aromatic alkyl group.Also particularly preferably be the alkyl of side chain, and have compared with same carbon number object straight chained alkyl, they cause a lower glass transition temperature T _g.

For the purposes of the present invention, particularly preferably being wherein this alpha-olefin is the copolymer with 2-EHA copolymerization.

Described acrylate and the mixture of methacrylate are same being applicable to.

The acrylate of this copolymer or methacrylate content are in the scope from 10wt% to 50wt%, preferably from the scope of 25wt% and 45wt%.

Especially the copolymer be applicable to is selected from and from Arkema (Arkema) at brand name is the group of obtainable material under EH, wherein some are also used as hot-melt adhesive.

Therefore, of the present invention is particularly preferably a kind of capillary method for reducing the fiber based on polyester or the fiber based on polyamide, it is characterized in that, a kind of E/X copolymer is added in this thermoplastic, and this mixture is spun into by melt-spinning process subsequently, this E/X copolymer be ethene and a kind of there are 6 to 30 carbon atoms the copolymer not replacing the acrylate of fatty alcohol, preferably E ethene and X mono-kind there is the copolymer of copolymer, more preferably E ethene and the X 2-EHA of the acrylate of 6 to 20 carbon atoms.

Therefore, of the present invention is particularly preferably a kind of capillary method for reducing the fiber based on polyester, it is characterized in that, a kind of E/X copolymer is added in this thermoplastic, and this mixture is spun into by melt-spinning process subsequently, this E/X copolymer be ethene and a kind of there are 6 to 30 carbon atoms the copolymer not replacing the acrylate of fatty alcohol, preferably E ethene and X mono-kind there is the copolymer of copolymer, more preferably E ethene and the X 2-EHA of the acrylate of 6 to 20 carbon atoms.

Therefore, of the present invention is particularly preferably a kind of capillary method for reducing the fiber based on polyamide, it is characterized in that, a kind of E/X copolymer is added in this thermoplastic, and this mixture is spun into by melt-spinning process subsequently, this E/X copolymer be ethene and a kind of there are 6 to 30 carbon atoms the copolymer not replacing the acrylate of fatty alcohol, preferably E ethene and X mono-kind there is the copolymer of copolymer, more preferably E ethene and the X 2-EHA of the acrylate of 6 to 20 carbon atoms.Have and indicate by the amount of the copolymer in the polyamide/polyester mixture of spinning processing is such as above to be added to needing, and if it be≤6wt% then by most of the cases find be enough.The concentration of this copolymer is preferably selected from the scope from 0.75wt% to 6.0wt% according to desired output speed (>700-1500m/min), makes the birefringence of this fiber be <3.510-3 like this.Such Fibre Birefringence allows draw ratio to be 1:5 and guarantees desired high line toughness (thread tenacities) under the spinning output speed do not considered up to 1500m/min in rolling (wind-up) speed being obviously greater than 3800m/min.

Can the amount of 0.001wt% to 5.0wt% material that routine is added, preferably dyestuff, other water-repelling agent, delustering agent, stabilizing agent, antistatic additive, lubricant, branching agent add in thermoplastic-copolymer mixture of the present invention safely.

The dyestuff that can preferably use is disperse dyes, specifically azo-based dyestuff those or based on those of the unusual carbon black of fine dispersion.

The delustering agent that can preferably use is the crystallite anatase of the particle mean size [d50] with 0.25 μm to 0.35 μm, and it also can have organic or inorganic surface treatment.

The stabilizing agent that can preferably use comprise such as aromatic poly-carbodiimide (such as Stabaxol P, from Mannheim, Germany Rhein Chemie Corporation (Rheinchemie of Mannheim,), and also have based on the heat stabilizer of organic phosphorous acid ester derivant Germany).

The antistatic additive that can preferably use is the conduction level carbon black of fine dispersion or CNT in particular.

The lubricant that can preferably use LCFA in particular, preferably stearic acid Huo behenic acid, its esters, preferably calcium stearate or zinc stearate, and also have its ester derivant class, and also have low molecular weight polyethylene wax and/or polypropylene wax.The mixture of that montan wax is the straight chain of the chain length with 28 to 32 carbon atoms in implication of the present invention, saturated carboxylic acid.Preferred lubricant and/or releasing agent be from low molecular weight polyethylene wax class group and also have from having the saturated of 8 to 40 carbon atoms or undersaturated aliphatic carboxylic acid class and the compound of group with the representative examples of saturated aliphatic amine of 2 to 40 carbon atoms or the amide-type of alcohols or ester class.For the purposes of the present invention, very particularly preferably be ethylene bis stearamide and pentaerythritol tetrastearate (PETS).Especially, pentaerythritol tetrastearate (PETS) is very particularly preferred.

The branching agent that can preferably use is fusible modified bisphenol A epoxy chloropropane resin, such as Araldite GY764CH or Araldite GT7071, from the fertile Burger Heng Zi Man (Huntsman of Everberg, Belgium) of Belgium Chinese mugwort.

According to the present invention have copolymer to be used and this polyamide/polyester matrix polymer by compounding, preferably by blending constituent in an extruder, by using static mixer or being mixed by other suitable devices that two or more components can be mixed with each other.This melt is also optionally extruded by one-tenth stock, is cooled and be granulated.

Masterbatch technique is also possible, and in this case, this copolymer is as a kind of concentrate or mix with polyester granules as pure material.

But directly can also mix these independent components in spinning or melt-blown facility, in that case, these components also or respectively by two or more charging aperture can be imported by a charging aperture as a kind of physics premix.Another feasible possibility they is joined in a subflow of this matrix polymer, and then this subflow is mixed in the main flow of this matrix polymer.Advantageously, before this melt blend enters forward in independent spinning place and spinning mould by product dispensation line, to be set up a kind of distribution of restriction at this by duration of specific selection blender and this married operation.Discovery had 16sec ^-1to 128sec ^-1the blender of shear rate be favourable.In fact, by by this shear rate (sec ^-1) be multiplied by 0.8 of this time of staying (in second) ^ththe product that power produces should be preferably 250-2500, more preferably from the scope of 350 to 1250.Usually the value being greater than 2500 is avoided, so that the Pressure Drop in restriction conduit engineering circuit.For avoiding query, can it is to be noted that also use term polymer to mention this thermoplastic at this.

At this, shear rate is restricted to the shear rate (sec on surface ^-1) being multiplied by the blender factor, this blender factor is a characteristic parameter of the blender of the type.Such as, for Sulzer SMX type, this factor is about 7-8.The shear rate γ on this surface is according to following calculating

$\mathrm{\&gamma;}=\frac{4\&CenterDot;{10}^3\&CenterDot;F}{\mathrm{\&pi;}\&CenterDot;\mathrm{\&delta;}\&CenterDot;R^3\&CenterDot;60}\left[{\sec }^{-1}\right]$

And this time of staying is according to following calculating

$t=\frac{V_2\&CenterDot;\mathrm{\&epsiv;}\&CenterDot;\mathrm{\&delta;}\&CenterDot;60}{F}$

Wherein

F=polymer pump transmission rate (g/min)

V ₂internal volume (the cm of=blank pipe ³)

The diameter (mm) of R=blank pipe

ε=void volume mark (for Sulzer SMX type from 0.84 to 0.88)

Nominal density (the about 1.2g/cm of the polyblend of δ=in the melt ³).

Not only the mixing of these polymer but also the spinning of this polymeric blends subsequently exist usually, depend on this matrix polymer, preferably more preferably carrying out from the temperature of 30 DEG C to 70 DEG C in the scope of 5 DEG C to 85 DEG C, each is higher than the melt temperature of this matrix polymer.It is be from 225 DEG C to 300 DEG C from 265 DEG C to 340 DEG C and for nylon-6 and PBT that preferred temperature is arranged for PET.

Such as produce a melt-blowing equipment from the fibrous nonwoven webs having thermoplastic to be used to produce according to the present invention.One of them extruder is for heating these components and making them reach a high pressure.After optional coarse filtration by an applicable filter assemblies, then extrude this melt by a spinning head by spinning pump with the speed of accurate measurement.This polymer leaves-is also called weaving term filament-be still simultaneously melting form from Die and mould plate as a kind of fine fibre.Air stream makes this filament cool and stretches it simultaneously still in melt state.This filament is sent on such as one conveyer belt being configured to sieve or on porous bucket or on the substrate entered such as sensitive paper by this air stream.Suction below this sieve band causes these lines to become fixing.The fibre sheet of this random arrangement is that a kind of needs are by the fibrous nonwoven webs of consolidation.Consolidation can such as by two heating rollers (calender) or undertaken by a vapor stream.When a calender is used for carrying out consolidation, one of two rollers have the depiction be made up of point, short rectangle or Diamond spot usually.These filaments merge at contact point and therefore form this non-woven fabric.The non-woven fabric that relative weight is light is obtainable by means of only this technology (hot adhesion), and the heavy non-woven fabric of relative weight is produced in through the process of a so-called fixing heating furnace by this hot-melt adhesive of melting with the polymer of a kind of second low melting point combined, and this matrix fiber adheres to each other to guarantee the toughness desired by this nonwoven thus in their crosspoint usually.Consolidation is possible further by Hydroentangled (hydroentangling) method, wherein the jet impact of water still unconsolidated fabric under the hydraulic pressure up to 400 bar.This melt-blown process typically uses following parameter manipulation:

Fibre diameter 0.1 μm is to 20 μm, preferably 1 to 10 μm

Fabric width is up to 5000-6000mm

Temperature 230 DEG C is to 400 DEG C, preferably 290 DEG C to 370 DEG C

The air speed 0.5-0.8 velocity of sound doubly

Basis weight 8g/m ²to 350g/m ², typically 20g/m ²to 200g/m ²

Hole in spinning head to 500 μm, this spinning head has 1 to 6 hole/mm

High tenacity filament preferably has the mixture based on thermoplastic to be used from according to of the present invention, preferably this polyamide/polyester mixture, by spinning under >700m/min, output speed more preferably in the scope from 750m/min to 1000m/min, and drawing under respective rate, heat cure and rolling are produced.The known spinning means of this use itself complete.

The polyamide/polyester filament of high tenacity is produced in large-scale direct melt-spun facility typically via this melt-spinning process, and wherein this melt is assigned to independent yarn (spinline) and the independent spinning unit within these yarns by the product line of heating.Yarn is a series of a line or multirow spinning unit, and a spinning unit is the minimum spinning unit with spinning head (spinhead), and it comprises at least one spinning mould spinning box (comprising spinning Die and mould plate).Under melt is exposed to high-caliber thermal stress in such a system, the time of staying is up to 35min.Need to be subject to indistinctively for reducing the validity of capillary copolymer the impact of the high thermal stability result due to this copolymer according to the present invention, so additive even in a small amount, such as <2.0% and in most of the cases even <1.5% be enough, no matter high this depend on the thermal stress of desired capillary reduction-.

Mould spinning box to be used is had preferably to have every meter of die width at least 20, more preferably from 150 to 1500 and even more preferably from 500 to 1000 die holes according to the present invention.Die orifice diameter from 0.05mm to 1mm and especially from 0.3mm to 0.5mm is preferred.

Die exit velocity is preferably in the scope from 1m/min to 20m/min, but more preferably from 3m/min to 10m/min.The blowing stream (blowing stream) of hot-air causes the line extruded to be drawn as preferably from their length after mould outlet of 50 to 800 times, causes spinning speed up to 10000m/min.

At least one copolymer that the invention still further relates at least one alpha-olefin and at least one acrylate or methacrylate is for reducing based on the fiber of thermoplastic or filament, preferably based on the fiber of polyester or filament or based on the fiber of polyamide or filament, more preferably based on the fiber of polyester or the capillary purposes of filament.

The invention further relates to the capillary fiber or filament with reduction, these fibers or filament be added with the fiber based on thermoplastic of at least one copolymer of at least one alpha-olefin and at least one fatty alcohol acrylate or methacrylate by melt-spun or filament obtainable.

The invention still further relates to the capillary fiber based on thermoplastic from reduction of the present invention, preferably based on the fiber of polyester or filament or based on polyamide fiber or the filament surface tension of reduction (often kind all have) obtainable product, preferably fibrous nonwoven webs, nonwoven, weaven goods, stretch ring knitted fabric, non-crimped fabric or forming ring knitted fabric, fibrous nonwoven webs or nonwoven especially, these fibers or filament are added with at least one copolymer of at least one alpha-olefin and at least one acrylate or methacrylate.

For the sake of clarity, be to be noted that and comprise above with generic term or all definition enumerated with preferred compositions and parameter with any desired combination in the context of the present invention.

Usually, the surface tension of fiber can be determined from their wettables from liquid (polarity is different).Determine that the mode possible according to the capillary another kind on the fiber product of the present invention's acquisition relates to the adsorption dynamics adsorption kinetics of a kind of liquid medium (such as water or cyclohexane) that the applicable tensometer of use one is absorbed by this fiber product with detection.

example

Capillary being reduced in injection mould making sheet according to the material of the present invention's acquisition is confirmed quantitatively, and confirmed qualitatively on the fibrous nonwoven webs obtained by melt-blown process, these injection mould making sheet are used for capillary Accurate Measurement as molding-system.

Injection mould making sheet is determined the surface tension reduced:

Illustratively described in the present invention surface tension reduces, and first prepares corresponding mold compound.To this; by these independent components at a double screw extruder (ZSK 26Mega proportioning machine; from section doubly grand Werner and Pu Fulai Durel Corporation (Coperion Werner & Pfleiderer) (Stuttgart; Germany (Stuttgart; Germany) mix at the temperature)) between 250 DEG C with 285 DEG C; become stock to extrude, be cooled to the point that can be granulated, and be granulated.After dry (at 80 DEG C of dry 2-6h of cardinal principle in vacuum drying chamber), these pellets are processed into test specimen.

These test specimens (rectangular slab size 60*40*4mm or 150*105*1.0mm) for the test reported in tables 1 and 2 are produced on the injection molding machine of an Arburg 320-210-500 type under the melt temperature of about 260 DEG C and under the molding temperature of about 80 DEG C.

The surface tension of the rectangular slab obtained from material produced according to the invention be according to DIN ISO 8296 service test ink with one simple and reproducible mode determine.

The surface tension obtained according to DIN ISO 8296 is usually incomparable with the value obtained according to ASTM D 2587-84.Surface tension value is reported with nN/m (=dyn/cm).

This test method is by the wetting degree of the ink with different surfaces tension force based on the polymer surfaces of evaluation test sample.The spreader being attached to bottle cap is immersed in this test ink, this bottleneck limit (bottle rim) and for immediately this ink being applied to the surface in test of nuzzling up.Length of stroke should be at least 100mm.The behavior at this stroke edge is assessed in the length of 90%, so do not consider minimum inhomogeneities.Be less than within two seconds if this ink stroke narrows down to, then this measurement must use a kind of ink with more low surface tension to repeat until these edges continue two seconds.If this ink stroke keep being greater than two seconds constant, then this measurement must use and have higher capillary ink and repeat until realize two seconds.The value then this bottle shown corresponds to the surface energy of this breadboard.This test under 23/50 standard conditions, namely must be carried out under the temperature of 23 DEG C of +/-2 DEG C and the relative humidity of 50%+/-10%.

Test of the present invention uses from Hamburg, Germany Suo Futa Electronics Co., Ltd. (see Suo Futa report numbers 108) (Softal Electronic GmbH, (see Softal Report No.108), Hamburg, Germany) test ink carry out.

Fibrous nonwoven webs determines surface tension:

In order to reduce the surface tension on thermoplastic fiber in the manner of the present invention, using a device for melt blowing to produce and there is about 55g/m ²the fibrous nonwoven webs of basis weight.These tests are carried out under the melt temperature of about 275 DEG C and under the thermal air current of about 360 DEG C.The ratio between melt throughput and volume of air flow velocity of selection to obtain the average fibre coarseness of about 1 μm from the mould diameter of 300 μm.The fibrous nonwoven webs described in the example with contrasting of the present invention is only different in used concrete polymer composition, example of the present invention for often pair and contrast, every other parameter and therefore non-thermoplastic parameter (such as basis weight, pore size, fibre orientation and fibre coarseness) keep identical.

For capillary qualitative evaluation, water droplet is applied on these fibrous nonwoven webs.This fabric is shown high surface tension level (hydrophilic behavior) by water droplet quick humidification, and the droplet profile of reservation on a surface illustrates low surface tension level.In order to realize further differentiation, air stream is applied on this drop.If this drop leaves a vestige with the form of moisture film, then it can be summarized as surface tension qualitatively relatively high; If this drop is crossed over this fibrous nonwoven webs and moved and do not stay next visible washmarking mark, then can be summarized as relatively low surface tension level (see table 3).

Following component is employed in test:

Component A1: there is about 69cm ³the straight chain polybutylene terephthalate of/g (at 1:1 phenol at 25 DEG C: measure in 1,2-dichloro-benzenes) inherent viscosity ( b 600, the bright Sheng German company (Lanxess Deutschland GmbH, Leverkusen, Germany) from Leverkusen, Germany city)

Component A2: there is about 94cm ³the straight chain polybutylene terephthalate of/g (at 1:1 phenol at 25 DEG C: measure in 1,2-dichloro-benzenes) inherent viscosity ( b 1300, the bright Sheng German company from Leverkusen, Germany city)

Component A3: there is about 80cm ³the PET copolymer (PETplus 80, the PET Kunststoffrecycling GmbH company from German Bei Sailixi-upper Di Fenba) of/g inherent viscosity.

Component A4: nylon-6 ( b40F, the bright Sheng German company from Leverkusen, Germany city)

B component 1: the copolymer of ethene and 2-EHA, this copolymer have 63wt% ethylene moiety and 550 MFI ( 37 EH 550, from the general urban Arkema (Arkema, Puteaux, France) of France) [CAS No.26984-27-0]

B component 2: 35 BA 320: the copolymer of ethene and n-butyl acrylate, this copolymer have 65wt% ethylene moiety and 320 MFI ( 35 BA 320, from general urban Arkema of France) [CAS No.25750-84-9]

The wettable of the attachment of water droplet serious this fabric of reducing and water along with the fact that the concentration increasing B component 1 seriously reduces indicates and therefore indicating reduces for the surface tension in the polyester fiber of this fabric.For realizing hydrophobic decisive increase, only the B component 1 of 1wt% is exactly enough.

Claims (10)

1. for reducing based on the fiber of thermoplastic or the capillary method of filament, it is characterized in that, this thermoplastic is added with at least one alpha-olefin and has the acrylate not replacing fatty alcohol of 6 to 30 carbon atoms or the E/X copolymer of methacrylate and be spun into by melt-spinning process, and wherein used thermoplastic is polyamide or polyester.

2. method according to claim 1, it is characterized in that, the polyester used is polyalkylene terephthalates, preferably polyethylene terephthalate, polytrimethylene terephthalate or polybutylene terephthalate, more preferably polybutylene terephthalate and polyethylene terephthalate, special most preferably polybutylene terephthalate, or the mixture of these terephthalate.

3. method according to claim 1, is characterized in that, the polyamide used is fatty polyamide.

4. according to the method in any one of claims 1 to 3, it is characterized in that, mixture is used for spinning, and these mixtures are copolymers of at least one thermoplastic based on 99.9 to 10 weight portions and 0.1 to 20 weight portion.

5. method according to any one of claim 1 to 4, is characterized in that, these alpha-olefins have the carbon atom between 2 and 10 and can be unsubstituted or replaced by one or more aliphatic, alicyclic or aromatic group.

6. method according to claim 5, it is characterized in that, alpha-olefin is selected from the group comprising following item: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 3-Methyl-1-pentene, preferred alpha-olefin is ethene and propylene, ethene is very particularly preferred, and also has the mixture of these alpha-olefins.

7. the method according to any one of claim 5 and 6, is characterized in that, the alpha-olefin content of this copolymer is between 50wt% and 90wt%, preferably between 55wt% and 75wt%.

8. method according to any one of claim 1 to 7, it is characterized in that, with the interpolation material of the amount of 0.001wt% to 5.0wt% by routine, preferably dyestuff, other water-repelling agent, delustering agent, stabilizing agent, antistatic additive, lubricant, branching agent add in this thermoplastic-copolymer mixture.

9. method according to any one of claim 1 to 8, it is characterized in that, this thermoplastic is added with a kind of E/X copolymer, this E/X copolymer be ethene and a kind of there are 6 to 30 carbon atoms the copolymer not replacing the acrylate of fatty alcohol, preferably E ethene and X mono-kind there is the copolymer of copolymer, more preferably E ethene and the X 2-EHA of the acrylate of 6 to 20 carbon atoms.

10. at least one alpha-olefin and acrylate or methacrylate E/X copolymer for reducing based on thermoplastic, preferably based on the fiber of the thermoplastic from polyamide or polyester race or the capillary purposes of filament.