CN1302923A - Polyester fiber possessing low pilling tendancy and its manufacturing method - Google Patents

Abstract

The present invention relates to a polyester fibres with reduced tendency to pilling formation, the polyester fibres contains polyester which can form long fibres, the polyester fiber comprises: at least 90 mol.% polyethylene terephthalate; an aliphatic or alicyclic diol which can degrade the polyester to a relative viscosity of 1.37 to 1.58 in 1w% cresol; 0.003 to 1.0 w% (relative to polymer forming long fibre) silicon dioxide or silica particle finely dispersed in polyester materials and 0.003 - 2.0 w% (relative to polymer forming long fibre) silicon oil. At least portion of the active groups (if exist in the silicon oil) is connected to the polyester molecular by chemical bond.

Description

Play polyester fiber and manufacture method thereof that proclivity reduces

The present invention relates to the polyester fiber of a kind of ANTIPILLING (pill resistant) or low balling-up (low-pill), and particularly relate to a kind of belonging to and have the height that has reduced proclivity significantly and hanged down ball-type.The present invention more relates to the method that a kind of manufacturing has the polyester staple fiber of reduction balling-up (pilling) tendency.

For the feature of the balling-up effect of describing fiber, warp resistance abrasiveness (the flexing abrasionresistance) is measured by so-called metal wire wear test usually.Fixedly allowing filament on lametta, reciprocally move under the tension force, even the filament wearing and tearing are till fracture.Because the diameter of metal wire has the identical order of magnitude (20-40 μ m) with the diameter of fiber, (please refer to " TextilePrufungen " the 4th edition of Stefan Kleinheinz institute works and make strong bending stress (flexingstress) combine with corrasion, in June, 1991, by Akzo Fiber Division, Wuppertal, german publication; U.S. Pat-A-5, the 858,529, the 3rd hurdle, the 54th to 65 row).Known metal wire wearing and tearing intermediate cycle value (the wire abrasion stroke cycles that does not have the pet fiber (polyethyleneterephthalate) of ANTIPILLING character; The WASC value) be generally between 3000 to 5000, yet the WASC value of the fiber of low balling-up character is less than 2000.

Make dress-goods with polyester fiber, for example suit, shirt or jacket can have durable, dimensionally stable, crease recovery, exempt to press the advantage of character.

Have high stability and good abrasion resistance by the made textiles of these fibers, make the clothes of dress be difficult for balling-up.Aspect textiles, " balling-up " meaning the formation of fubril ball, for example the brief summary of clothing surface or coccoid thing.These coccoid systems stretch out clothing surface by fiber ends or lax pars fibrosa and coiling institute is produced, and owing to the high toughness of fiber, make these coccoid things be attached to clothing surface and are difficult for falling.Therefore, the appearance of clothes is damaged easily, thereby reduces the availability (please refer to German patent DE-A-27 13 508) of clothes.

Therefore, improving polyester staple fiber (the plyester staple fibers) raw material properties that is used to produce clothes is that its necessity is arranged, so that these fibers are difficult for balling-up or almost completely avoid balling-up.

Propose many eliminations or reduced balling-up or the method for a proclivity.

A known method has low-molecular-weight polyester, for example low solution viscosity (relative viscosity) for weaving.In spinning extruder (spinning extruder), make the spent glycol additive, please refer to U.S. Pat-4,359,557.Through reducing intensity (tenacity), abrasion resistance and bending resistance, the durability of transporting a little coccoid things with obvious reduction.The number average molecular weight of polyester (number average molecularweight) (please refer to MelliandTextilber.1970, p.181 with the counter-bending abrasiveness of fiber is approximately linear; Chemiefasern+Text.Anwendung-stechnik Text.-Ind.23 (1973), p.181).With the effect that has reduced proclivity its limit is being arranged aspect actual the utilization by reducing molecular weight.For obtaining to avoid the polyester fiber of balling-up, melt viscosity need be reduced to the spinning no longer feasible (with Textilpraxis international, in April, 1984,374 pages of comparisons) under the molten condition.Therefore, can't obtain to avoid the polyester textile of balling-up by aforesaid method.Therefore, the objective of the invention is to seek a kind of additive, this additive has reduced proclivity, reduces the melt viscosity of polyester simultaneously not obviously.

The another kind of known method of making the polyester fiber of low balling-up is to sneak into the composition (branching components) that contains side chain in polycondensation reaction.With multivalence (multivalent) carboxylic acid or alcohols, for example trimethylolpropane (Textilpraxis International 1993, p.29; DE-OS 2-046 121), pentaerythrite (No. the 901716th, Canadian Patent) or other branching agents, change the character of polyester.By described chemical modification, can shorten macromolecular length, but because high weight average molecular weight (weight average ofthe molecular weight) can be kept high melt viscosity, the result reduces the degree of resistance to wearing and bending resistance curvature of fiber, and then has reduced proclivity.The use of branching agent was narrated in many patents, and for example patent FR-A-1 603 030.Yet if consider that from indefectible (spinning faultlessness) aspect of spinning these methods cause some important problem, and one of them is short mouth (spinnerets) service life of spinning.In addition, the further processing that influences the converter ribbon owing to the not enough cleaning of spinning completely has problems.To have its difficulty by make the fine-titred low balling-up fiber product that has less than 3 dtexs with the polyester of above-mentioned chemical modification.

Another kind of known method is with special chemical bond, be mainly-the Si-O-key (being called the SiO-key hereinafter) to incorporate polyester chain into, but this chemical bond does not participate in reaction, just can be hydrolyzed in the processing procedure that water or steam are arranged in follow-up spinning process.This kind method both can obtain the polyester of the required melt viscosity of melt spinning method, carries out easily again, thereby, when the hydrolysis in final spinning process takes place, could be through reducing molecular weight, to reduce balling-up trend.Many patents are addressed in making the polyester process additive that divalence and multivalence are contained Si and are incorporated polyester chain into by condensation reaction, whereby with silicon-organic compound, for example with tetraethyl orthosilicate (tetraethyl silicate) or phosphoric acid silantriol (silanetriol) ester as modifier (modifiers).

U.S. Pat-A-3,335, describe in 211 to make and have the polyester staple fiber that improves anti-pilling, and that this polyester staple fibers maintains by the anhydrous polyethylene terephthalate with melt viscosity 100 to 600Pas (under 275 ℃) is made, and every mole of ethylene glycol contains the silicon atom of 0.10 to 0.75 gram in this polyethylene terephthalate.Esters of silicon acis (silicate esters) for example for being dissolved in ethylene glycol mesosilicic acid tetra-ethyl ester, is incorporated in the polymeric chain in polycondensation reaction.European patent EP-A-0 262 824 advises that similarly with polyester fiber modification (modification), MODIFICATION OF POLYESTER FIBER is to reach by the water treatment of tetraethyl orthosilicate and following process.

German patent DE-A-17 20 647 similarly advises in polycondensation process ester and salt, trihydroxy silicon ethane (silanetrilethane) phosphate for example, and particularly, incorporate polyester chain into by the diethylester (diethylesters) of trimethoxy silicon ethane phosphoric acid.

German patent DE-A-27 13 508 and DE-A-24 53 231 suggestions will be that 0.008 to 2 diphenyl dihydroxy silane (diphenylsilanediol) is incorporated in the polyethylene terephthalate as common component (co-component) with respect to the percentage by weight of dimethyl terephthalate (DMT) (dimethylterephthalate) in polycondensation reaction.

The PET series that German patent DE-A-41 11 066 describes with the modification of SiO-base gets terephthalic acid (TPA) (terephthalic acid) via direct esterification effect constantly (directesterification).Silicic acid methoxyl group ethyl ester or silicic acid propyl ester are sneaked into polymer, make that the silicone content of polymer is 300 to 700ppm.This is to get the person by constantly add silicic acid methoxyl group ethyl ester or silicic acid propyl ester in polycondensation reaction, and the weight average molecular weight of performed polymer (prepolymer) is between 9000 to 16000 gram/moles, polydispersity (polydispersity) index between 1.5 to 2, temperature between 260 to 290 ℃ and pressure between 1.5 to 2.5bar.Duration of the reaction between silicate and the performed polymer needs 5 minutes at least.

The balling-up fiber of exempting from that is provided on the market is to make according to said method, and the method is the silicon compound of sneaking in polycondensation reaction hydrolysis sensitivity (hydrolysis-sensitive).Because to the hydrolysis sensitivity, almost be unique method that is applied in these successive reactions at present based on ester exchange reaction (transesterification) method of dimethyl terephthalate (DMT).Yet,, increase sizable degree of difficulty because of in esterification, producing water if use the main at present direct esterification method of using.When carrying out production method, still need face other problems.For the melt viscosity (melt viscosity) that obtains polyester to a certain degree relative final viscosity (relative end viscosity) with finished fiber, reduced certain amount with respect to this relative terminal viscosity of initial relative viscosity, polyester must be adjusted to a fixing degree of polymerization earlier before spinning, and the SiO-key of the hydrolysis sensitivity (hydrolysis-sensitive) of fixed number must be incorporated in the polyester simultaneously.The number of the SiO-key of incorporating into is relevant with macromolecular number, and can determine the reduction degree of the relative viscosity after the spinning.This need control machined parameters and the amount of controlling the modifier that is added exactly very exactly in production of polyester.On the other hand, before spinning, polyester must keep anhydrous state utterly.Therefore, the polyester that contains the SiO-key often only can be used in (the granulating step in the middle of promptly not needing) in the direct fabrics process (direct spinning process), maybe needs to use additional special operational step.

U.S. Pat 5,858,529 have disclosed another kind of manufacture method, the polyester fiber made of method has high anti-ball thus, the polyester that wherein will contain percentage by weight and be a special poly alkylene glycol block copolymer (polyalkylene glycol block copolymer) of 1 to 7 carries out chemical modification, and this poly alkylene glycol block copolymer has hydrophobic polypropylene oxide (hydrophobicpolyoxypropylene) nuclear core and the polyethylene glycol oxide (polyoxyethylene) that is connected to the nuclear core.The method of this production staple fibre is the polyester (normal polyester) and block copolymer (blockcopolymer) of elder generation with standard, carries out spinning again.

Aforesaid method all has shortcoming, these methods or the special modification of polyester perhaps need be needed fiber or textiles are carried out special subsequent processing steps.

The chemical modification of above-described polyester, for example use trimethylolpropane, pentaerythrite, oxirane propylene oxide block copolymer (ethyleneoxide propylene oxide block copolymers) to carry out modification or the SiO-key is incorporated in the polymer chain, additional shortcoming is arranged, and this shortcoming is for adding chemical modifier in the polyester condensation process or before the condensation.Therefore, these modifier can pollute reactor, thereby make production equipment can't be used in dissimilar polyester.For present successional polycondensation reaction unit, it generally can be produced polyester and reach 600 tons/day, but can produce too many useless transition material (transition material) if change prescription, make that the operator scheme of this polycondensation reaction unit is uneconomic.

One possibility that must can not influence the pilling property of polyester via chemical modification is to add additive before spinning process or in the spinning process.Silicone oil (silicone oils), for example dimethyl silicone polymer (polydimethylsiloxanes) or PSI (polymethyl phenylsiloxanes), the additive that can be used as polymer in the spinning process (please refer to Textilpraxis International, in April, 1984, the 374th, 375 page).In this publication, with percentage by weight is that (temperature is 20 ℃ for the polysiloxanes (polysiloxanes) of 0.1-2%, range of viscosities 100 is to 500mPas) mix in the charging hopper of fused mass extruder (melt extruder), it is mixed with the polyester of commercially available granule, in spinning under 290 to 295 ℃ of the mouth temperature, extrude and make it to become silk in this mixture again.Said method can reduce counter-bending abrasiveness (flexing abrasion resistance) significantly.PES filament after the modification is subjected to crooked wearing and tearing stress and splits into single fibrillation (fibrils).Since this kind division, and cause the fibrillation premature breakage.When incorporating silicone oil into polyester parent (matrix) with the form of inert substance, the engineering properties of fabric changes and is not obvious.Percentage elongation during fracture (elongation) is influenced hardly with the original dimensions unit (module) of intensity (tenacitv) and fiber.If compare with pure polyester fused mass, polyester/polysiloxane mixture (containing the polysiloxanes up to 1.8% weight ratio) demonstrates the reduction degree of melt viscosity less than 5%.

Patent DD 104 089 description adding molecular weight can increase melt viscosity less than the DC resin (silicone resins) (methyl phenyl silicone methylphenylpolysiloxanes) of 4000 gram/moles, and can easily spin low molecular polyester, and can produce the low balling-up polyester fiber of WASC value about 900.According to patent DD104 089, but will include several esterifications-silicone resin of OH base adds in the polycondensation reaction, and forms branched structure, thereby increase macromolecular weight average molecular weight.In patent DD104 089, when introducing branch's modifier (branched modifying agents), the reduction that plays proclivity is attributable to above-mentioned effect.

But lack esterification-existing its main shortcoming of polysiloxanes (polysiloxanes) tool of OH base, as pure inert additwe, in further process, polysiloxanes can migrate to fiber surface, thereby negative effect is arranged, as in dyeing course.And, additive wash out (wash out) result, make the ANTIPILLING effect scatter and disappear.Use polyfunctional group (polyfunctional) silicone oil (but for example have more than 2 esterifications-the OH yl) and the branch's thing that forms also has shortcoming, if consider that from indefectible and spinning cleaning (spinning cleanness) aspect of spinning branching agent can have problems.

The another kind of known additive that is used for polyester is silica SiO ₂, reduced proclivity with silica, need additional processing method.In fact synthetic SiO 2 powder is generally used for giving thixotropy, is as dispersant, thickener (increase melt viscosity) and anti-blocking agent (anti-blockingagent) (in film).

According to German patent DE-A-29 09 188, the silica dioxide granule or colloidal silica (colloidal silica) particle that will have 1 to 100nm diameter are incorporated polyester into, and the air spots that can eliminate the spinning poly ester fiber is smooth.

According to Japan Patent JP-A-55 112-313, if operating weight percentage is 0.5 to 10% silica (silica; Particle size is less than or equal to 80nm), can reduce the proclivity that rises of special copolyester fiber (wherein 0.1 to 10% ester bond is a phosphate).Yet described specific process need carry out subsequent treatment to polyester fiber with hot water, steam and/or solvent.

According to patent DE 1 237 727 and patent DD 104 089, colloidal silica in polycondensation reaction with the form of suspended substance as additive.Moisture need be got rid of fully till the beginning spinning, melt viscosity can be increased with the method.If use and similarly above-mentionedly to incorporate the chemic modified method of polyester into, need carry out subsequent treatment to polyester fiber with hot water, steam and/or solvent with the water-disintegrable pure SiO-key of tool.

According to the method for having addressed at present, SiO 2 powder directly added the polyester fused mass or add do not get rid of in the polyester granulate of moisture, can obtain the polyester fiber of low pilling tendency with the method.The present invention at first proposes a kind of standard polyester (standardpolyesters) that will can buy on the market with pure SiO 2 powder and carries out modification, to have reduced the manufacture method of proclivity.And employed silica among the patent DE-A-404 1042, only with being the speed of spinning that increases the POY spinning machine.

According to purpose of the present invention, propose a kind of low balling-up of tool economy or exempt from the manufacture method of the polyester fiber of balling-up, and the particularly relevant standard polyester that can buy on the market, be the polyester of raw material with ethylene glycol (ethylene glycol) particularly, and a small amount of suitable additive of adding carry out modification to described polyester in an advantageous manner in spinning process with terephthalic acid (TPA) (terephthalic acid).The result is, after spinning, can reduce proclivity significantly according to the polyester fiber of method manufacturing of the present invention.Fiber production method of the present invention is more or less the same with general polyester processing,, can produce described fiber and without any problem with the existing equipment of fiber production producer that is.

According to claim 1 of the present invention, by the polyester fiber of a kind of ANTIPILLING and low balling-up is provided, according to claim 14 of the present invention, the manufacture method of the polyester fiber by a kind of ANTIPILLING and low balling-up are provided can solve described problem.Have the polyester fiber of the present invention that has reduced proclivity and have the defined composition of claim 1, thereby by the combination of three kinds of different modifier, the anti-pilling that improves fiber with beyond thought important way is important.

According to the present invention, three kinds of additives that use together with standard polyester are: 1. dihydroxylic alcohols (diol), dihydroxylic alcohols are selected from the group that ethylene glycol (ethylene glycol), diethylene glycol (DEG) (diethylene glyocl) and triethylene glycol (triethylene glyocl) are formed; 2. silicone oil (silicone oil); And 3. SiO 2 powder or silicon oxide powder (silica powder).

The present invention is with fiber Trevira ^_350 comparison yardsticks as anti-pill fibre.Consider Trevira from the anti-pilling aspect ^_350 fiber quality, Trevira ^_350 WASC value is less than 700, and the present invention promptly obtains and Trevira in favourable and economic mode first only by additive is made an addition in the standard polyester ^_The fiber of 350 same quality.This is because the additive silicone oil has different operation mechanisms with silica, and causes the generation of cooperative effect (synergistic effect).Manufacturing method according to the invention, the fiber number of fiber be 2.4 dtexs with the situation of thinner 1.7 dtexs under, can obtain to have the WASC value of highly hanging down balling-up, (embodiment 16 and embodiment 18 in the table 5) as shown in table 1.

Table 1

Fibre count (fiber number)	2.35 dtex	1.69 dtex
			Intensity	2.92cN/ dtex	2.90cN/ dtex
Percentage elongation	52％	48％
			WASC	618	696

Test via spinning widely, aforesaid additive 1. to 3. of the present invention is added in the commercially available standard polyester, no matter be the certain polyester fiber (the WASC value is less than 700) that obtains to have highly low balling-up of combination adding of indivedual addings or 1. and 2. or 1. and 3..But if consider from economic face and the indefectible aspect of spinning, based on three kinds of additive capacities that added, proclivity to a WASC value that only can reduce polyester fiber with the combination of described additive is about about 1000, and in the prior art and describe this inventive features.

As unique additive, it is 1200 that multipotency reduces anti-pilling to WASC value, and reaches the limit of spinnability (spinnability) with ethylene glycol.The amount approximately linear (as shown in Figure 1) of WASC value and the ethylene glycol that added.

Known have many silicone oils, and these silicone oils are all with for sliding agent (gliding agent) or lubricant (lubricating agent).Common silicone oil for example is polydialkysiloxane, poly-diaryl silica and polyoxyethylene alkyl aryl radical siloxane.The silicone oil that the present invention preferably uses is dimethyl silicone polymer, for example is Baysilon ^_M 1000.But preferred silicone oil is the silicone oil with end esterified hydroxy groups, but and wherein is preferably the dimethyl silicone polymer of the OH-base with end esterification.

Get rid of crosslinked (cross-linkages) effect in advance, but the present invention uses the silicone oil of the OH-base with two esterifications, but more preferably have the silicone oil of the OH-base of two end esterifications, preferably corresponding dimethyl silicone polymer.Struktol ^_The silicone oil of polydis 3999 belongs to this type, is Hamburg, Germany Schill ﹠amp; The Seilacher manufacturing be the dimethyl silicone polymer of terminal groups with the dihydroxy.The described example of Fig. 2 shows with the dimethyl silicone polymer that lacks the OH-base compares, and described silicone oil increases the effect of the anti-ball of polyester fiber.Compared to the silicone oil of other type, Struktol ^_Silicone oil more can improve the indefectible property of spinning and the spatter property of spinning.And, have now found that, if only use silicone oil separately or use silicone oil simultaneously with ethylene glycol as the additive of polyester, then along with the increase of silicone oil content, the meeting that influences of a proclivity and WASC value is reduced (as shown in Figure 2) significantly.

Use the particularly preferred silicone oil of the present invention, for example Struktol ^_With use can degrade immediately (degradation) polyester and ethylene glycol, metal wire wearing and tearing stroke periodic quantities (WASC value) can reach in 1000 the scope (comparison diagram 2), but need by adding a large amount of additives, could obtain this scope, not satisfy the requirement of highly low balling-up fiber.Even be added in the Struktol shown in Fig. 2 simultaneously ^_The highest addition and percentage by weight be 0.1% ethylene glycol, the WASC value still can't reach about value below 900.

Be similar to the correlation of the addition of WASC value and silicone oil, also can observe, as additive, along with the addition increase of silica, the WASC value can reduce significantly, but can only be reduced to a particular value with silica.Even add ethylene glycol simultaneously, with the highest addition at the silica shown in Fig. 3, the WASC value still can't reach about value below 1000.Only obtain described value, but still do not meet the requirement of highly low balling-up fiber by adding a large amount of silica.Because if use a large amount of silica, can't allow silica with in the poly-ethyl ester of required fractionized adding.And this can cause spinning the increase of mouth place accumulation of pressure, thereby shortens the service life of spinning mouth, or blocks spin mouth hole.Therefore, according to the present invention, preferably the amount with silica maintains percentage by weight below 1%, and preferred weight percentage ranges is between 0.05 to 0.3%, and by suitable hybrid element (mixing elements) SiO 2 powder is sneaked in the polyester equably.

Therefore, the existing discovery, the dioxide-containing silica of WASC value and interpolation or with the silicone oil content of independent interpolation or not linear with the correlation of the silicone oil content that adds ethylene glycol and silicone oil simultaneously.No matter the combination of the combination of ethylene glycol and silica or ethylene glycol and silicone oil, the addition of additive is identical with the fundamental relation of WASC value in each case.After content of additive in the fiber arrives a particular value, its influence very little (as Fig. 2 and shown in Figure 3) to the WASC value.In order to obtain WASC value less than 1000, then need to add a large amount of silica (with ethylene glycol) or silicone oil (with ethylene glycol), yet in the former, can reduce the quality of spinning and influence following process, all can excessively increase the price of product in both cases.

According to claim 14 of the present invention, the problems referred to above have been solved by the method for the present invention that produces the described polyester fiber that has hanged down proclivity.Therefore, the present invention also relates to a kind of manufacture method, the modification that wherein is used in equal polyester (homopolyester) and copolyesters (copolyester) in the manufacturer's standard textile fabric usually is to obtain by introducing modifier in the polyester fused mass suitably or before the fusion additive suitably being added in the dried particulate in extruder, and the polyester after the modification can be spun into low balling-up or exempt from the polyester fiber of balling-up thus.In manufacture method of the present invention, introduced term " Late AdditionTechnology " (with U.S. Pat-A-5,858,529 relatively).

About additive 1; The relative viscosity of polyester fiber of the present invention is generally 1.37 to 1.58, is preferably 1.40 to 1.55, most preferably is 1.42 to 1.48 (measuring in metacresol with 1%).In order to improve spinning properties (spinning performance), the present invention uses higher molecule polyester, and its relative viscosity for example is RV=1.65, and by inserting dihydroxylic alcohols, be ethylene glycol, diethylene glycol (DEG) or triethylene glycol for example, the required relative viscosity of this higher molecule polyester of degrading to described polyester.Therefore, need to use the aliphatic of respective amount or alicyclic dihydroxylic alcohols this higher molecule polyester of degrading respectively.With ethylene glycol is example, and amount ranges and is decided according to the initial viscosity of polyester usually between percentage by weight 0.03 to 0.28%.If use particulate, dihydroxylic alcohols can be added the charging zone of extruder or in the direct fabrics process, mix the fused mass pipeline.In preferable embodiment of the present invention, make spent glycol as dihydroxylic alcohols.

Manufacturing method according to the invention except making spent glycol, also comprises following ingredients, and with additive 2. and additive 3. expressions.

About additive 2; Interpolation is 0.003 to 2.0% with respect to the percentage by weight of employed polyester amount, is preferably 0.05 to 0.5% silicone oil.But do not contain esterification-the commercially available silicone oil of OH base, for example be the Baysilon that makes by Bayer company ^_M1000, its dynamic viscosity (dynamic viscosity) under 20 ℃ is 1400mPas.In order to utilize silicone oil to reduce the proclivity that rises of polyester fiber, particularly favourable in practice, according to the present invention, but preferred use has the silicone oil of the OH-base of two end esterifications.Be preferably the dimethyl silicone polymer of the dihydroxy end-blocking with terminal OH-base especially, its chemical formula is:

HO-[Si-O (CH ₃) ₂] _n-OHn=8-60, preferred n=40.(mean value of n=repeated monomer unit)

The silicone oil that is added is the degraded of impact polymer hardly.But but by hydroxyl and the polymer matrix of esterification to the esterification of small part, with respect to pure inertia polysiloxanes, in following process, described group can not migrate to the surface, thereby can not cause disturbing effect (interfering effect), for example in the dyeing course of fiber.Thereby also got rid of the danger that washes out additive.

But an example of the commercially available silicone oil of particularly preferred OH-base with end esterification is by Hamburg, Germany Schill﹠amp; The Struktol of Seilacher manufacturing ^_Polydis 3999, and the degree of polymerization of this silicone oil is n=40, and the dynamic viscosity of this silicone oil under 20 ℃ is 82mPas.By adding this silicone oil, can obviously improve the spinning function, i.e. the indefectible aspect of spinning and the cleaning aspect of spinning are (compared to not using Struktol ^_Spinning test).Therefore, this silicone oil can be used as very good inside and slides agent.High spir-draw ratio, promptly the speed of La Jin seal wire (pull-off godet) and the speed ratio that squeezes out spin mouth hole cause low molecular weight polyorganosiloxane oil Struktol probably ^_In fiber, arrange,, thereby improved anti-pilling significantly so that promote indivedual fibriilar divisions in the fiber in the mode of particularly advantageous similar fibrillation (fibril-like).

About additive 3; Adding percentage by weight is 0.003 to 1.0%, is preferably the synthetic silica powder of 0.05 to 0.3% segmentation, and the initial particle size of this SiO 2 powder (primaryparticle sizes) is less than 30 μ m.This is meant the SiO 2 powder of porous, and it is to be made by high temperature process (flame color hydrolysis, electric arc, plasma) or wet method (precipitated silica, silica gel).Be preferably especially and have the pyrolytic silicon dioxide of initial particle size less than 100nm.

Particularly preferred commercially available prod is as by the Aerosil of Frankfurt, Germany Degussa company by the manufacturing of flame color hydrolysis ^_200, Aerosil ^_300 or Aerosil ^_130 products.Another commodity, for example Syloid that makes for Grace company ^_, the synthetic silica of a kind of micron change (average initial particle size is 3-4 μ m).The function of silica of the present invention is not to be the increase melt viscosity as previously mentioned, but forms predetermined breakaway poing probably in fiber, and causes rupturing in the process of tension loading and torsional deflection.

Select as another kind, use and contain percentage by weight and be 1-15%, be preferably the masterbatch (masterbatch) of the silica of 5-15%.Thereby, masterbatch and additive add in the extruder in an advantageous manner or the polyester fused mass in, or masterbatch and additive are added in the particulate in advance by proper device respectively.

SiO 2 powder is blended among the PET, for example by so-called molten prepolymer processing method (meltconditioning method) continuously polyester fused mass modification (German patent DE 40 39 857 C2) is carried out.According to the molten prepolymer processing method, the fused mass of part is obtained from the main smelt flow of fused mass, and the fused mass of this part can directly get self-condensation reaction or obtain from melting appartus.This partial melting thing is sent into effluent extruder (side stream extruder), supply the silica additive herein, disperseed again.Subsequently, dispersion, mixed fusion concentrate flow back to main fused mass pipeline (melt line), then utilize the static agitator to make this fusion concentrate dilution, to form last concentration.Add silicone oil and ethylene glycol with liquid form.Before using the static agitator, these two kinds of liquid additives add in the main fused mass pipeline earlier.

And, if directly begin and in the spinning extruder, melt the PET particulate of this standard with standard P ET particulate, SiO 2 powder, silicone oil and ethylene glycol are directly added in the PET particulate in the spinning extruder, mix polyethylene terephthalate and additive, then again with mixture in addition spinning also be feasible.

As previously mentioned, can pure material or the mode of compounding substances or masterbatch add additive of the present invention or additive agent mixture.Material and the additive and the spinning that can add in addition, other interpolation.Polyethylene terephthalate itself can contain additive commonly used already, for example delustering agent (mattingagents) (titanium dioxide), stabilizing agent, catalyst or the like.Among the application " polyethylene terephthalate " (PET) or " polyester " mean polyester contain molar percentage at least be 90% polyethylene terephthalate unit and at most molar percentage be 10% from the dihydroxylic alcohols except ethylene glycol, it for example is diethylene glycol (DEG), 1,4-butanediol or from the dicarboxylic acids except terephthalic acid (TPA) for example is isophthalic acid (isophthalic acid), hexahydroterephthalic acid, dibenzo acid (dibenzo acid).

If desired, polyethylene terephthalate can be additionally with the already mentioned branching agent in a small amount of front, for example trimethylolpropane, trimethylolethane, pentaerythrite, glycerol, trimesic acid (trimesic acid), trimellitic acid (trimellitic acid) or pyromellitic acid (pyromellitic acid) modification in addition.Initial polyester also may comprise known additives, to improve colouring power, for example is 3, and 5-dicarboxyl benzene sulfonic acid sodium salt (sodium-3,5-dicarboxybenzenesulfonate).

The advantage of the inventive method for institute if having time in polycondensation reaction device can use identical standard set-up.After direct esterification effect or ester exchange reaction, can use textiles standard particulate.Only after polycondensation reaction, before spinning, add, so just can have high flexibility and economic efficacy because of the required additive of specific condition.Therefore, according to the present invention, the additive that will have required effect in the short time of staying (residence time) is sneaked in the polyester fused mass of high viscosity, and, also can not cause negative effect to spinnability without any need for polycondensation reaction condition (vacuumizing) to remove low molecular cleavage product (low-molecular splitting products).And these additives have stability, and can not be lavaged.

Below by the following example and accompanying drawing fiber of the present invention or its manufacture method are described in more detail, spinning machine and the drawing process (drawing method) of wherein making staple fibre are known for those of ordinary skills, for example be described in Ullmann's Encyclopedia of IndustrialChemistry (Ullmann industrial chemistry encyclopaedia), the 5th edition, Vol.A10, Fibers (fiber), 3.General Production Technology (general production technology), the 550-561 page or leaf.

Description of drawings:

Fig. 1 is shown to be the variation to the ethylene glycol content that added of the WASC value measured among the different embodiment, and wherein the WASC value is to record on fiber number is the polyester of 2.4 dtexs;

Fig. 2 is shown (to be respectively Struktol to the silicone oil that is added for the WASC value ^_, Baysilon ^_) dependence of content, Fig. 2 also shows WASC value and the silicone oil (Struktol that is introduced ^_) amount and the percentage by weight that adds simultaneously be the correlation between 0.1% the ethylene glycol;

Fig. 3 is shown to be the correlation that the percentage by weight of WASC value and dioxide-containing silica and interpolation simultaneously of the fiber of 2.4 dtexs is respectively 0.1%, 0.14% ethylene glycol for the fiber number of being measured among the different embodiment; And

Fig. 4 is shown for the fiber number of being measured among the different embodiment be the WASC value of fiber of 2.4 dtexs to the correlation of ethylene glycol, silica and the silicone oil content of interpolation, wherein the measurement point of WASC value in 500 to 700 scopes is particularly preferred scope of the present invention.

It is 1.65 weaving quality that the PET of embodiment 1 to embodiment 20 polyethylene terephthalate (PET) standard has relative viscosity

(in temperature is 20 ℃, measures in metacresol with 1%), and

Contain 0.3% titanium dioxide.Silicone oil is the dimethyl silicone polymer of terminal groups with the dihydroxy, and n=40 (is

Hamburg, Germany Schill﹠amp; The silicone oil of Seilacher manufacturing, the merchant

Product are called Struktol ^_Polydis 3999), lack the OH-terminal groups

Dimethyl silicone polymer, be the Bayer of German Leverkusen

The silicone oil of company's manufacturing, commodity are called Baysilon ^_M

1000 dihydric alcohol ethylene glycol (EG) SiO ₂Silica (silica of Degussa company manufacturing, commodity

Aerosil by name ^_200) mensuration of the mensuration WASC value of WASC value is according to U.S. Pat-A-5,858,529

The content that the 3rd hurdle is the 54th to 65 page is carried out experimental performance

Go up hybrid standard polyethylene terephthalate particulate and 0.3% silica TiO at melt-spun machine (melt spinning machine) ₂, make this mixture have relative viscosity 1.65 (in temperature is under 20 ℃, measures in metacresol with 1%), then fusing and mixture table 2 described additives.Under 258 ℃ of melt temperatures, be 599 gram/minute with output (throughput), tow (filaments) is spun mouth (spinneret) ejection by what have 845 apertures, and the diameter that spins the mouth aperture is 0.35mm.Then, (central quenching) condenses into silk by central chilling, then stretches with 891 meters/minute speed and puts in the canister.Then, firm spun fibre bundle (tows) with 3.2 times be stretching on the filamental thread (fiber line), is then curled, thermosetting, cutting short-forming fiber again.

Liquid parts (silicone oil and ethylene glycol) is directly mixed in the interior particulate inflow of spinning extruder.By metering device (by German Koch Maschinentechnik GmbH, Ispringen/Pforzheim company makes) mixed silica powder and particulate.Become in the example at great majority, silica is used as masterbatch (percentage by weight is 10% silica in polyester matrix).

Table 2

Embodiment	Fiber number [dtex] *	????EG **	Silicone oil	The ultimate density of silica in PET
					??1	????2.40	????0.14％
??2	????2.40	????0.14％	0.40％Struktol _
					??3	????2.40	????0.14％		??0.50％SiO 2
??4	????2.40	????0.14％	0.40％Struktol _	??0.50％SiO 2
					??5	????2.40	????0.14％	0.40％Struktol _	??0.20％SiO 2
??6	????2.40
					??7	????2.40		0.40％Struktol _
??8	????2.40		0.90％Struktol _
					??9	????2.40	????0.10％
??10	????2.40	????0.10％	0.40％Struktol _
					??11	????2.40	????0.10％	0.90％Struktol _
??12	????2.40	????0.10％		??0.20％SiO 2
					??13	????2.40	????0.10％		??0.50％SiO 2
??14	????2.40	????0.14％	0.40％Struktol _	??0.50％SiO 2
					??15	????2.40	????0.16％	0.40％Struktol _	??0.50％SiO 2
??16	????2.40	????0.16％	0.40％Struktol _	??0.20％SiO 2
					??17	????2.40	????0.14％		??0.20％SiO 2
??18	????1.67	????0.16％	0.40％Struktol _	??0.20％SiO 2
					??19	????2.40		0.60％Struktol _
??20	????2.40		0.40％Struktol _

^*Final fiber number ^*Ethylene glycol

Consider from the anti-pilling aspect, the purpose of these experiments is to obtain Trevira ^_350 fiber quality.Table 3 is listed Trevira ^_350 fibre property is with the standard of comparison as the polyester fiber of the present invention that uses same procedure to measure.

The relative value of table 3 fiber Trevira 350 (comparative value) (method according to table 1 is measured)

	Trevira _350	Trevira _350
			Fiber number [dtex]	????2.36	???1.64
Intensity [cN/ dtex]	????2.69	???2.64
			Percentage elongation [%]	????50.84	???28.46
WASC	????545	???655

Record at the following viscosity number that spins the tow of extruding under the mouth according to the present invention:

The viscosity (relative viscosity) of table 4 embodiment 1 to 20

Embodiment	Relative viscosity is measured in metacresol with 1%
		1	1.471
2	1.458
		3	1.456
4	1.446
		5	1.445
6	1.650
		7	1.641
8	1.630
		9	1.500
10	1.497
		11	1.493
12	1.490
		13	1.479
14	1.440
		15	1.436
16	1.432
		17	1.467
18	1.427
		19	1.638
20	1.631

Embodiment 6 representatives zero change, and promptly do not add any additives.

The weaving data of table 5 finished fiber

Embodiment	Fiber number [dtex]	Intensity [cN/ dtex]	Percentage elongation %	WASC *
					1	2.34	3.38	48.37	1382
2	2.31	3.36	48.66	932
					3	2.43	2.93	53.45	997
4	2.30	3.00	49.25	673
					5	2.40	3.07	54.27	715
6	2.42	4.02	48.79	3008
					7	2.41	3.98	54.50	1451
8	2.41	4.00	52.27	1304
					9	2.44	3.61	52.86	1649
10	2.31	3.68	53.01	990
					11	2.47	3.60	51.33	905
12	2.35	3.36	52.15	1208
					13	2.37	3.21	54.97	1140
14	2.31	2.90	53.01	622
					15	2.47	2.69	55.33	511
16	2.35	2.92	52.15	618
					17	2.43	3.09	54.72	1045
18	1.69	2.90	47.97	696
					19	2.37	3.90	52.10	2170
20	2.41	3.95	51.89	2273

^*WASC=metal wire wearing and tearing stroke periodic quantity (wire abrasion stroke cycles)

Can observe, manufacturing method according to the invention can obtain to have highly low balling-up WASC value, and fiber number is 2.4 dtexs and the fiber of thinner 1.7 dtexs, (embodiment 16 and embodiment 18 in the table 5) as shown in table 1.

Compared to Trevira ^_350 fibers, fiber number are that embodiment 14 to 16 and the fiber number of 2.4 dtexs is that the embodiment 18 of 1.7 dtexs meets all requirements (as shown in table 1).

Though the present invention has been carried out the present invention with embodiment preferred; right its is not in order to limit the present invention; any those of ordinary skills; without departing from the spirit and scope of the present invention; can carry out various variations and modification, so protection scope of the present invention is defined by appending claims.

Claims (16)

1. one kind has the polyester fiber that has reduced proclivity, comprising:

(1) polyester, as forming long stapled polymer, this polyester is that 90% polyethylene terephthalate unit is formed by molar percentage at least;

(2) dihydroxylic alcohols, this dihydroxylic alcohols are selected from the group of being made up of ethylene glycol, diethylene glycol (DEG), triethylene glycol, and the addition of this dihydroxylic alcohols polyester to the relative viscosity scope that is enough to degrade is 1.37-1.58 (measuring in metacresol with 1%);

(3) silicon dioxide granule or silicon oxide particle, silicon dioxide granule or silicon oxide particle are 0.003 to 1.0% with respect to the percentage by weight that forms long stapled polymer, silicon dioxide granule or silicon oxide particle are finely divided in polyester material;

(4) silicone oil, this silicone oil is 0.003 to 2.0% with respect to the percentage by weight that forms long stapled polymer, wherein exist in this silicone oil under the situation of a plurality of reactive groups, described reactive group to small part is connected on a plurality of polyester macromolecules by chemical bond-linking; And

(5) a plurality of additives that optionally add, this additive are that general known process is used or as the usefulness of specific use; It is 1.37-1.58 (measuring in metacresol with 1%) that wherein said polyester fiber has the relative viscosity scope.

2. polyester fiber as claimed in claim 1, wherein silica is finely divided porous silica powder.

3. polyester fiber as claimed in claim 1, wherein silica has initial particle size less than 30 μ m, is preferably less than 100 μ m.

4. as claim 1,2 or 3 described polyester fibers, wherein silica is to use with the form of masterbatch, and this masterbatch is based on polyester, and the percentage by weight of the silica that contains is 1 to 20%, is preferably 5 to 15%.

5. polyester fiber as claimed in claim 1, wherein this silicone oil is polydialkysiloxane, poly-diaromatic siloxane or polyoxyethylene alkyl aryl radical siloxane, is preferably dimethyl silicone polymer.

6. polyester fiber as claimed in claim 5 wherein uses the silicone oil with a plurality of reactive hydroxyls, and being preferably per molecule has two terminal-reactive hydroxyls.

7. as claim 5 or 6 described polyester fibers, wherein silicone oil is the dimethyl silicone polymer with two terminal hydroxyls.

8. as each described polyester fiber among the claim 1-7, wherein said polyester fiber has metal wire wearing and tearing stroke periodic quantity WASC less than 700.

9. as each described polyester fiber among the claim 1-8, wherein said polyester fiber has metal wire wearing and tearing stroke periodic quantity WASC less than 600.

10. as each described polyester fiber among the claim 1-9, wherein will gather terephthaldehyde institute glycol ester as forming long stapled polymer.

11. as each described polyester fiber among the claim 1-10, wherein employed silicon dioxide granule or silicon oxide particle are 0.05 to 0.3% with respect to the percentage by weight that forms long stapled polymer, and the percentage by weight of employed silicone oil is 0.05 to 0.5%.

12. as each described polyester fiber among the claim 1-11, the relative viscosity that wherein said polyester fiber has is 1.37-1.58, this relative viscosity is to be dissolved in metacresol measured with 1% weight these polyester fibers.

13. polyester fiber as claimed in claim 12, the relative viscosity that wherein said polyester fiber has are 1.42-1.48, this relative viscosity system is dissolved in metacresol measured with 1% weight this polyester fiber.

14. the manufacture method of a polyester fiber, the arbitrary as described above claim of this polyester fiber is described, wherein fusing before add in a plurality of polyester granules with the composition of (4) described additive (2), (3), or before spinning, join in the polyester fused mass, then mix or dispersion, subsequently with the spinning in addition of this molten mixture, to form this polyester fiber.

15. the manufacture method of polyester fiber as claimed in claim 14, wherein in order to carry out the continuous modification of polyester fused mass, this part polyester fused mass is obtained from the main flow of this polyester fused mass, and in this part polyester smelt flow to effluent extruder, silica or silicon oxide powder are added in this polyester fused mass in this effluent squeezer, and disperseed therein, disperse, mixed fusion concentrate flows back in the main fused mass pipeline, then utilize the static agitator to make this fusion concentrate dilution, to form final concentration, before using the static agitator, add the ethylene glycol and the silicone oil of liquid form earlier, subsequently described molten mixture is spun into silk.

16. polyester fiber as claimed in claim 1, wherein with have relative viscosity greater than 1.55 polyester as benchmark, by adding aliphatic or alicyclic dihydroxylic alcohols, with the predeterminated target viscosity (relative viscosity of this polyester degraded to this polyester, weight with 1% is dissolved in the metacresol measured), and this predeterminated target viscosity is between 1.40 to 1.55, is preferably between 1.42 to 1.48.

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