CN104619897B - Moisture absorption type polyester fiber and preparation method thereof - Google Patents
Moisture absorption type polyester fiber and preparation method thereof Download PDFInfo
- Publication number
- CN104619897B CN104619897B CN201380045855.XA CN201380045855A CN104619897B CN 104619897 B CN104619897 B CN 104619897B CN 201380045855 A CN201380045855 A CN 201380045855A CN 104619897 B CN104619897 B CN 104619897B
- Authority
- CN
- China
- Prior art keywords
- polyester fiber
- polyester
- moisture absorption
- poly
- absorption type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of moisture absorption type polyester fiber and preparation method thereof, in this polyester fiber, containing poly N-vinyl lactams moisture absorption composition and phosphorus is heat stabilizer, wherein poly N-vinyl lactams accounts for 3～15wt% of polyester fiber weight, and it disperses footpath is below 200nm; Phosphorus is the content of heat stabilizer accounts for polyester fiber weight 50～500ppm in P element. When poly N-vinyl lactams and polyester blend, using L/D is two more than 45 axle extruder blend at a lower temperature, and spinning at a lower temperature, obtains polyester fiber. Phosphorus is that heat stabilizer adds in the time of blend or when melt spinning. The tone that the polyester fiber finally obtaining has good durable hygroscopicity, fiber is good, and light fastness excellence, can be used for underwear or motion dress material.
Description
Technical field
The present invention relates to a kind of moisture absorption type polyester fiber and preparation method thereof. Specifically, by adding in polyesterAdding moisture absorption composition and phosphorus is heat stabilizer, obtains being applied to the moisture absorption of the dress material such as underwear, sweat shirt materialProperty polyester fiber.
Background technology
Polyester fiber is typical thermoplastic synthetic fiber, since being born, due to its mechanical strength, resistanceMoral character, heat resistance etc. are good, aspect dress material and industry, are being widely used.
But the absorb-discharge humid of polyester fiber is extremely low, can not discharge in time sweat, in directly contact skin or subsidesWhen nearly skin is worn, have the sensation being clamminess, therefore limited polyester fiber sending out in interior clothing dress material purposesExhibition.
Improving the hygroscopic method of polyester fiber for example has in polyester copolymerization enter moisture absorption composition or interpolation has moisture absorptionThe compound of property. For example, in pet reaction process with on side chain, there is the glycol copolymerization of hydroxy alkylidene glycol,Or with methods such as the dicarboxylic acids copolymerization that contains metal organic sulfonate. But, the damp absorbent polyester fibre that combined polymerization obtainsThere is intensity and the low problem of weatherability in dimension.
Except above-mentioned by give fibrous raw material polyester with hygroscopicity, fiber is had hygroscopic method, alsoCan hygroscopic compound be attached on polyester fiber by chemical method. For example in rear process to knittingPolyester fiber in thing carries out acrylic or methacrylic acid grafting, then replaces carboxyl wherein with alkali metal, fromAnd the hygroscopicity of raising polyester fiber. But because hygroscopic compound is attached on fiber surface, usingIn journey, there is the problems such as intensity declines, feel is bad, light resistance is poor.
Japanese kokai publication hei 2-99612 disclose a kind of using hydroscopicity be more than 10% hygroscopicity resin as core,Conventional polyester is as the core-sheath-type composite fibre of sheath portion. The fiber obtaining is in this way doing refining, dyeing etc.When heat treatment, because the hygroscopicity resin of core segment easily absorbs water and expands, can form crackle at fiber surface, andDue to hygroscopicity resin to the dissolubility of water high and outwards flow out, make hygroscopicity disappear.
In the flat 8-311326 of the special Willing of Japan, disclose polyvinylpyrrolidone has been added in nylon to improve nylon fibreThe technology of dimension wettability power. The interpolation of polyvinylpyrrolidone can not produce negative interaction to the performance of nylon fiber,But polyvinylpyrrolidone is added in polyester and by its Fibrotic technology and has no and reported.
Summary of the invention
The object of the present invention is to provide a kind of moisture absorption type polyester fiber and preparation method thereof, by adding in polyesterAdd hygroscopic matter poly N-vinyl lactams, make its differential in polyester loose, thereby raising polyester fiberHygroscopicity. And in order to obtain the fiber of excellent color tone, light fastness excellence, in this fiber, also addPhosphorus is heat stabilizer.
Technical solution of the present invention is:
A kind of moisture absorption type polyester fiber, contains polyester, poly N-vinyl lactams moisture absorption one-tenth in this polyester fiberDividing with phosphorus is heat stabilizer, and wherein poly N-vinyl lactams accounts for 3～15wt% of polyester fiber weight, its pointLoose footpath is below 200nm; Phosphorus be heat stabilizer content in P element account for 50 of polyester fiber weight～500ppm。
In described polyester fiber of the present invention, with respect to the weight of polyester fiber, poly N-vinyl lactamsContent be 3～15wt%. In the time that the content of poly N-vinyl lactams in polyester fiber is less than 3wt%, fibreDimension does not have enough hygroscopicity, and practical application is poor; When containing of poly N-vinyl lactams in polyester fiberWhen amount exceedes 15wt%, fiber has sticky sense, very uncomfortable when contact, and fibrous physical property declines. In order to make to gatherEster fiber obtains more preferably moisture-absorption characteristics, and preferably the content of poly N-vinyl lactams is 5～12wt%.
The average dispersion footpath of poly N-vinyl lactams in described polyester fiber of the present invention should 200nm withUnder, preferably below 150nm. The average poly N-vinyl lactams of footpath below 200nm that disperse can be withPolyester fiber is complexing well, thereby can suppress the stripping of poly N-vinyl lactams, prevents polyester fiberHygroscopicity decline, improve the moisture absorption durability of polyester fiber.
Poly N-vinyl lactams described in the present invention can be for example NVP,The polymer of the N-vinyl lactam classes such as N-vinyl-2-piperidones, N-caprolactam.From the viewpoint of have less sterically hindered, easily adsorb and emit hydrone, in the present invention, doFor described poly N-vinyl lactams, preferably use the polymer of NVP, poly-Vinylpyrrolidone (PVP).
In the present invention, preferably using K value is 15～90 polyvinylpyrrolidone. More preferably use K valueIt is 20～70 polyvinylpyrrolidone. If the K value of polyvinylpyrrolidone is too low, polyvinylpyrrolidineThe complexing power of ketone and polyester is not strong, and in the Cooling Process after extruding, easily stripping, causes fiber to can not get veryGood hygroscopicity. And if its K value is too high, the viscosity of polyester system increases greatly, mixing spue bad,Be difficult to granulation, cause production efficiency low.
In polyester fiber described in the present invention, also contain in P element be equivalent to 50 of polyester fiber weight～The phosphorus of 500ppm is heat stabilizer. In the present invention, be heat stabilizer by adding phosphorus, can suppress polyester and existDuring with the blend of moisture absorption composition, there is thermal degradation and hydrolyzable, improve the tone of gained polyester fiber, improve itLight fastness.
Described phosphorus is that heat stabilizer can be phosphoric acid class, phosphorous acid class, phosphonic acid based, phosphoric acid ester etc. Specifically canThere are phosphoric acid, trimethyl phosphate, triethyl phosphate, tricresyl phosphate phenolic aldehyde, phosphorous acid, a phosphorous acid front three with what enumerateEster, methyl acid phosphate, phenolic aldehyde phosphoric acid, diphenylphosphoric acid, methyl acid phosphate methyl esters, phenolic aldehyde etherophosphoric acid, diphenylPhosphoric acid phenolic aldehyde ester, phosphoryl ethyl acetate, distearyl pentaerythritol diphosphate, two (tertiary fourth of 2,4,6-tri-Base phenyl) pentaerythritol diphosphate, resorcinol-bis-(two (pentaerythrite)) phosphate, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate or two (2,4-di-tert-butyl-phenyl) season pentaTetrol bisphosphate etc.
Described phosphorus is that heat stabilizer is preferably the bisphosphate based compound shown in formula 1:
R in formula1、R2Independently of one another for can there is substituent aromatic hydrocarbyl. Described aromatic hydrocarbyl is preferredFor C6～C10 aromatic hydrocarbyl, described substituting group is C1～C6 alkyl, amino, hydroxyl and sulfo group for example.Described R1And R2Can be for example phenyl, a position have phenyl that carbon number is 1～5 alkyl substituent,To alkyl phenyl, the aryl radical that can be replaced by amino or the aryl radical that can be replaced by sulfo group etc. In the present invention,R1、R2Be preferably independently of one another the one in the group of formula 2～formula 4 as follows:
When bisphosphate based compound shown in above-mentioned formula 1 uses as stabilizing agent, it is to polyester fiber toneImprove better effects if, thereby become preferably.
Two (2,6-di-t-butyl-4-aminomethyl phenyl) in bisphosphate based compound shown in above-mentioned formula 1Pentaerythritol diphosphate or two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate are used as stabilizing agentTime, its to polyester fiber tone to improve effect good especially, thereby most preferably.
The polyester using is in the present invention not particularly limited, for example, can be aliphatic polyester, can be also virtueFragrant adoption ester. Conventionally, mainly formed by binary acid repetitive and dihydroxylic alcohols repetitive.
Dihydroxylic alcohols repetitive can be aliphatic diol or aromatic diol particularly, as ethylene glycol, the third twoThe straight or branched aliphatic two of alcohol, butanediol and isomers thereof, pentanediol and isomers thereof, C6～C20Alcohol and isomers thereof, bisphenol-A and oxirane addition product, polyethylene glycol, polypropylene glycol, polytetramethylene glycol,One or more in cyclobutanediol, ring pentanediol, cyclohexanediol, benzene dimethanol, naphthalene dimethanol etc.
Binary acid repetitive can be specifically malonic acid, succinic acid, glutaric acid, adipic acid, C7～C20Alicyclic diacid and isomers thereof, terephthalic acid (TPA) and esterification derivative thereof, M-phthalic acid and esterification thereof are derivativeThing, containing C8～C18 aromatic acid such as other binary acid, naphthalene diacid or derivatives thereof of phenyl ring.
As the polyester using in the present invention, preferably fusing point is the polyester of 200 DEG C～240 DEG C, i.e. the fusing point of polyesterTm is more than or equal to 200 DEG C and is less than or equal to 240 DEG C. Poly N-vinyl lactams at high temperature heat resistance is poor,With the easy flavescence of fiber tone obtaining after polyester blend. Therefore, in order to make good hygroscopicity and excellent color tonePolyester fiber, processing needs as far as possible to control and carries out at a lower temperature. So select the polyester of low melting point passableReach this effect.
Described fusing point is that to be preferably polyethylene terephthalate be polyester, poly-to benzene to the polyester of 200 DEG C～240 DEG CDioctyl phthalate propane diols is that polyester, polybutylene terephthalate are polyester.
More preferably also contain the polyethylene terephthalate system of dihydroxylic alcohols copolymerization units and/or binary acid copolymerization unitsPolyester, poly terephthalic acid propane diols are that polyester, polybutylene terephthalate are polyester.
The dihydroxylic alcohols repetitive of copolymerization can be aliphatic diol or aromatic diol, preferably propane diols, fourthOne or more in glycol, bisphenol-A and ethylene oxide adduct.
The binary acid repetitive of copolymerization can be aliphatic dibasic acid, aromatic acid or their derivative.Derivative can be the methyl esters, ethyl ester, propyl ester of above-mentioned binary acid etc., preferably the methyl esters of binary acid. Aliphatic twoUnit's acid is preferably the representative examples of saturated aliphatic binary acid of carbon number 3～20, most preferably is malonic acid, succinic acid, pentaOne or more of diacid, adipic acid, azelaic acid; Aromatic acid is preferably M-phthalic acid or naphthalene diformazanAcid. Copolymerization binary acid repetitive of the present invention most preferably is M-phthalic acid or M-phthalic acid sulfonate unit.
Most preferably also contain the polyethylene terephthalate of sulfonate copolymerization units and/or polyethers copolymerization repetitiveBe that polyester, poly terephthalic acid propane diols are that polyester, polybutylene terephthalate are polyester.
The sulfonate composition of copolymerization can be M-phthalic acid 5-sodium sulfonate, M-phthalic acid 5-Sulfonic Lithium,Phthalic acid 5-sulfoacid calcium, ethylene isophthalate 5-sodium sulfonate, ethylene isophthalate 5-Sulfonic Lithium, ethylene isophthalate 5-sulfoacid calcium, DMIP 5-sodium sulfonate, isophthalic twoOne or more in formic acid dimethyl ester 5-Sulfonic Lithium, DMIP 5-sulfoacid calcium.
The polyether components of copolymerization can be one or more in polyethylene glycol, polypropylene glycol, polytetramethylene glycol.
In the situation that not affecting effect of the present invention, described polyethylene terephthalate is polyester, poly-to benzene twoFormic acid propane diols is that polyester, polybutylene terephthalate are in polyester, to comprise benzenetricarboxylic acid, benzene tetramethylThe polyfunctional copolymerization repetitives such as acid, glycerine, pentaerythrite.
Described polyester can be produced with industrial normally used polymerization, first carries out esterification or esterExchange reaction, obtains after low-molecular-weight petchem, then further under high temperature high vacuum, carries out polycondensationReaction, obtains polymer. Can add catalyst in esterification or ester exchange stage, described catalyst for contain sodium,The compound of the metallic elements such as lithium, magnesium, calcium, manganese, titanium, zinc, cobalt or tin, preferably containing these metallic elementsAcetate, most preferably titanate ester compound.
The invention still further relates to a kind of preparation method of above-mentioned polyester fiber, in the method, by polyester and poly-N-Vinyl lactam is to carry out blend, wherein poly N-ethylene on two more than 45 axle extruders at draw ratio L/DThe addition of base lactams accounts for 3～15wt% of polyester fiber weight; At the beginning of the blend melt spinning obtaining is obtainedRaw fiber, further stretches this as-spun fibre and obtains polyester fiber; On blend stage or melt spinning rankThe phosphorus that Duan Tianjia accounts for polyester fiber weight 50ppm～500ppm in P elements is heat stabilizer.
It is mixing that the present invention adopts L/D to be that more than 45 two axle extruders carry out, and can improve acyl in poly N-vinylThe dispersiveness of amine in polyester, makes it disperse footpath to reach below 200nm, and then improves the spinnability of blend.If L/D less than 45, can make poly N-vinyl lactams dispersion footpath increase, after spinning process in,There will be the problems such as frequent fracture of wire, fibrous physical property be bad.
On the other hand, because the vitrification point of most poly N-vinyl lactams is near 170 DEG C, mixedRefining and spinning temperature must be set on this temperature, allow poly N-vinyl lactams have good mobility.Therefore, in the present invention, preferably using fusing point is the polyester of 200 DEG C～240 DEG C, its can with poly N-ethyleneThe blend at a lower temperature of base lactams, when mixing, control fusing department temperature than melting point polyester temperature high by 10～In the scope of 20 DEG C, kneading part temperature is 180～230 DEG C. From in addition, poly N-vinyl lactams is at airIn easily water suction be clamminess, therefore can add water cooling plant at blending extrusion machine spout, control the temperature of spoutSpend below 80 DEG C, thereby feeding is carried out smoothly.
It is 15～90 polyvinylpyrrolidone that the present invention preferably uses K value. The polyethylene of K value within the scope of thisThe easier blend of pyrrolidones and polyester, strong with the complexing power of polyester, in the Cooling Process after blending extrusionBe not easy stripping, can obtain the good polyester fiber of hygroscopicity; In addition, the poly-second within the scope of this with K valueThe viscosity stabilization of the polyester system after alkene pyrrolidone blend, can not produce mixing spue bad, granulation is difficult,The problem of the low grade of production efficiency. More preferably the K value of polyvinylpyrrolidone is 20～70.
In the present invention, phosphorus is that heat stabilizer can add in the time of blend, also can in melt spinning process, add,Its addition is the 50ppm～500ppm that is equivalent to polyester fiber weight in P element. Preferably in the blend stageAdding phosphorus is heat stabilizer. Add heat stabilizer in the blend stage, by the shear action in blend, make heat steadyDetermine agent dispersed, can farthest bring into play its thermostable effect to matrix. Meanwhile, homodisperse heatStabilizing agent can not exert an influence to melt spinning afterwards.
In described method of the present invention, melt spinning preferably carries out at a lower temperature, particularly, preferably spinsSilk temperature is 220 DEG C～270 DEG C, more preferably 235 DEG C～260 DEG C. Spinning under lower temperature conditions, canReduce the decomposes of each blend components, thereby obtain the fiber of excellent color tone.
In the present invention, the hygroscopicity parameter Δ MR of preferred described moisture absorption type polyester fiber more than 1.0%, lookAdjust b value below 5.0, light fastness is more than 3 grades. The strength and elongation of this fiber is amassed more than 15.0, toolThe mechanical property that has general dress material purposes to use.
In the present invention, obtained polyester fiber is evaluated with following methods.
(1) mixing stability
Judge by the extrusion swelling degree of observing outlet of extruder place polyester. Without extrusion swelling be designated as zero,Slight extrusion swelling be designated as △, being designated as of serious extrusion swelling ×, wherein zero and △ be judged to be qualified.
(2) spinnability
Spinning situation in spinning 2 hours is evaluated by following method, without fracture of wire be designated as zero, have fewAmount fracture of wire (1～3 time) be designated as △, being designated as of fracture of wire frequent (more than 4 times) ×, wherein zero and △ judgeFor qualified.
(3) the average dispersion footpath of poly N-vinyl lactams
With vertically cutting fibre of length direction, get monofilament cross-sectional slice and carry out ruthenium dyeing, use transmission electron microscopyBlend state is observed, taken to mirror (TEM) (100,000 times). Fiber presents with continuous matrix composition (whitePart) for sea component, taking sub-circular the composition (gray component) that disperses as the island structure of island component.Regard island component as circle, converse diameter from island component area. Using this diameter as the polyethylene that forms island componentThe dispersion footpath of base pyrrolidones, using the mean value of 20 island components as average dispersion footpath.
(4) poly N-vinyl lactams K value
It is 1% the aqueous solution that poly N-vinyl lactams is mixed with to mass concentration, measures its relative viscosity, thenCalculate its K value with fikentscher,
logZ＝C[75K2/(1+1.5KC)+K]，
Wherein K:K value × 103, C: concentration of aqueous solution (W/V%), Z: the phase of the aqueous solution that concentration is CTo viscosity.
(5) strength and elongation of fiber is long-pending
Amass=intensity × (degree of stretching) of strength and elongation0.5，
Stress/the fiber number (cN/dtex) of maximum disrumpent feelings some when intensity is fibre stress-strained tensile, degree of stretching is fineTie up the strain (%) of maximum disrumpent feelings point.
(6) hygroscopicity parameter Δ MR
From fiber, remove finish, the sample of about 1g is put into the measuring cup that glass weight is W, be placed in dryIn dry machine, be dried 2 hours in 110 DEG C. By this measuring cup sealing, be placed in drier cooling 30 minutes. SurveyThe measuring cup weight W of sample is housed surely1. Then, put into and be set in 20 DEG C, 65%RH with open stateIn constant temperature and humidity machine, place 24 hours. Subsequently, then under sealing state, in drier, place 30 minutes.Then, again measure measuring cup weight W2. Continue to put into and be set in 30 DEG C, 90%RH with open stateIn constant temperature and humidity machine, place 24 hours, then in drier, place after 30 minutes under sealing state, then surveyDetermine measuring cup weight W3，
MR1＝(W2-W1)*100％/(W1-W)，
MR2＝(W3-W1)*100％/(W1-W)，
ΔMR＝MR2-MR1。
(7) light fastness
Test according to Japanese JISL-0842 standard, the higher expression color fastness to light of progression is better.
(8) mensuration of hygroscopic matter and content thereof in fiber
Record characteristic peak positions and the intensity of hygroscopic matter according to the hydrogen spectrum of nuclear magnetic resonance, then push away according to chemical formulaCalculate the content of this hygroscopic matter.
(9) tenor in polyester
6g polymer is pressed into sheet, and with fluorescent x-ray analysis apparatus, (x-ray that electric corporation of science manufactures dividesAnalysis apparatus 3270 types) measure its intensity, change with the detection line that the sample of known metal content makes in advanceCalculate.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
By dimethyl terephthalate (DMT), Sodium Dimethyl Isophthalate-5-sulfonate (SIPM), ethylene glycol, ownDiacid and as the butyl titanate of catalyst, adds in esterifying kettle, wherein the addition of SIPM be equivalent to rightThe 2.6mol% of rutgers addition, the addition of adipic acid is equivalent to dimethyl terephthalate (DMT) to be addedThe 5.4mol% of dosage, the addition of butyl titanate is equivalent to the 10.5ppm of copolyesters in titanium elements, by rightRubbing of total sour composition that rutgers, SIPM and adipic acid form and glycol component (ethylene glycol)You also add than being 1: 1.8 the manganese acetate that is equivalent to copolyesters 200ppm in manganese element in esterifying kettle simultaneously;Under 230 DEG C, condition of normal pressure, react 4 hours, methyl alcohol obtains little point after distillating and point reaching more than 95%The prepolymer of son. Prepolymer is remained under 230 DEG C, normal pressure, add in P elements and be equivalent to copolyesters 50ppmPhosphorus be stabilizing agent phosphoric acid, after 5 minutes, start decompression, heat up. Make temperature rise to 290 by 250 DEG C with 90 minutesDEG C, Pressure Drop is to 80Pa. After stirring, be back to normal pressure to importing nitrogen in reaction system, stop polycondensation reaction,Obtain thus fusing point and be the polyester of 230 DEG C.
The polyvinylpyrrolidone that is 30 by K value (PVP, BASF AG's product), two (tertiary fourth of 2,6-bis-Base-4-aminomethyl phenyl) pentaerythritol diphosphate exists with the polyester that the fusing point that obtains with said method is 230 DEG CThe upper blending extrusion of two axle extruders (φ 44mm, L/D:52). Wherein, the addition of PVP accounts for polyester fiber3wt%, the addition of bisphosphate is equivalent to the 150ppm of polyester fiber in P elements. The temperature of extruderBe set as 245 DEG C of fusing departments, 200 DEG C of kneading parts. Extrude in order. In gained blend, PVP's is averageDispersion footpath is 80nm. The blend obtaining is carried out to melt spinning, and spinning temperature is 255 DEG C, and spinning speed is2500m/min, obtains as-spun fibre, then as-spun fibre is obtained to polyester fiber by 2.2 times of deep processings. RightThis polyester fiber carries out the evaluation of above-mentioned parameters and performance. The results are shown in table 1.
Embodiment 2～4
Change respectively the PVP addition with respect to polyester fiber into 5wt%, 10wt%, 15wt%, other are sameEmbodiment 1. Evaluation result is in table 1.
Comparative example 1～2
Change respectively the PVP addition with respect to polyester fiber into 1wt%, 20wt%, other are with embodiment 1.Evaluation result is in table 1.
Table 1
The demonstration of table 1 result, in embodiment 1～4, the hygroscopicity parameter Δ MR of gained polyester fiber is 1.1More than %, tone b value is below 4.8, and strength and elongation is amassed below 19.8, and light fastness is more than 3 grades.In embodiment 1～3, mixing stability and spinnability are good, in embodiment 4, and mixing stability and spinningProperty reaches real requirement. On the other hand, at comparative example 1, be 1wt with respect to the PVP addition of polyester fiber%, reaches real requirement although mixing with spinning, and the hygroscopicity of gained fiber is bad. In comparative example 2,PVP addition with respect to polyester fiber is 20wt%, and when mixing, extrusion swelling is serious, granulation difficulty.
Embodiment 5～8
Change the PVP addition with respect to polyester fiber into 7wt%, with respect to polyester fiber in P elementThe addition of two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate change into respectively50ppm, 250ppm, 350ppm, 450ppm, other are with embodiment 1. Evaluation result is in table 2.
Comparative example 3
Be heat stabilizer except not adding phosphorus, obtain fiber by the method identical with embodiment 5. Evaluation resultIn table 2.
Comparative example 4
Terephthalic acid (TPA), ethylene glycol and the catalytic antimony trioxide are added in esterifying kettle to terephthalic acid (TPA) and secondThe mol ratio of glycol is 1: 1.8, under 230 DEG C, condition of normal pressure, carries out esterification 4 hours, obtains little moleculePrepolymer. Prepolymer is remained under 230 DEG C, normal pressure, add in P elements and be equivalent to copolyesters 50ppmStabilizing agent phosphorus compound phosphoric acid, after 5 minutes, start decompression, heat up. Temperature is risen with 90 minutes by 250 DEG CTo 290 DEG C, Pressure Drop to 80Pa. After stirring, be back to normal pressure to importing nitrogen in reaction system, stop polycondensationReaction, obtains fusing point and is the polyester of 252 DEG C thus.
With respect to polyester fiber, PVP addition is 7wt%, two (2,6-di-t-butyl-4-aminomethyl phenyls)The addition of pentaerythritol diphosphate is counted 150ppm with phosphorus element content.
Melting temperature is 265 DEG C, and spinning temperature is 280 DEG C. Evaluation result is in table 2.
Table 2
The demonstration of table 2 result, in embodiment 5～8, hygroscopicity parameter Δ MR, the tone b of gained polyester fiberLong-pending and the light fastness of value, strength and elongation and mixing stability and spinnability are all good. On the other hand, comparingIn example 3 and 4, the tone b value of gained fiber is respectively 6.0 and 10.0, and fiber light fastness is respectively 3Level is following and 1 grade.
Embodiment 9～11
Select draw ratio L/D to be respectively 45,48,55 two axle extruders and carry out blend, other are with embodiment 5.Evaluation result is in table 3.
Comparative example 5～6
Select draw ratio L/D to be respectively 30,35 two axle extruders and carry out blend, other are with embodiment 5. CommentValency the results are shown in Table 3.
Table 3
Table 3 result shows, in embodiment 9～11, and in gained polyester fiber, polyvinylpyrrolidone flatMonodispersed footpath is below 180nm, and the average dispersion footpath of the polyester fiber of embodiment 11 is little of 90nm. And than, in example 5 and 6, the average dispersion footpath of polyester fiber is more than 250nm. Show to use specific draw ratio/D'sTwo axle extruders are significant to the average dispersion footpath of the polyvinylpyrrolidone in control polyester fiber.
Embodiment 12
Get terephthalic acid (TPA) 5.7Kg, butanediol 5.4Kg, polyethylene glycol (molecular weight 4000) 3.75Kg carries outAfter fully mixing, drop into stir and the reactor of heated for controlling temperature in, and add catalyst metatitanic acid four butyl ester 8g and15g antioxidant IR1010, is warmed up to 230 DEG C of esterifications of dewatering gradually, and esterification yield reaches 95%And when above, finish esterification, and be warming up to gradually 250 DEG C, reduce reaction pressure to 130Pa simultaneously,Deviate from little molecular reaction, reach after the polymer viscosity of setting, the blank that spues, obtains fusing point and is 220 DEG CPolyester.
The PVP that is 60 by K value (BASF AG's product) squeezes at two axles with the polyester that above-mentioned fusing point is 220 DEG CGo out blending extrusion on machine (φ 44mm, L/D:52), wherein the addition of PVP accounts for the 7wt% of polyester fiber,The Temperature Setting of extruder is 235 DEG C of fusing departments, 180 DEG C of kneading parts, extrudes in order. In gained blendThe average dispersion footpath of PVP is 100nm. The blend obtaining is carried out to melt spinning, in spinning process, addTwo (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, its addition is equivalent to polyester fibre in P elementsThe 150ppm of dimension. Spinning temperature is 245 DEG C, and spinning speed is 2000m/min, obtains as-spun fibre, then willAs-spun fibre obtains polyester fiber by 2.4 times of deep processings. To the evaluation result of gained polyester fiber in table 4.
Embodiment 13～14
The fusing point of selecting fusing point to be respectively to be made by embodiment 1 is that the polyester of 230 DEG C and fusing point are 240 DEG CPolyester (except adipic acid addition is equivalent to the 4.0mol% of terephthalic acid (TPA) methyl esters addition, is pressed and enforcementThe method that example 1 is identical makes), the spinning temperature while changing melt spinning is accordingly respectively 255 DEG C, 260 DEG C,Other are with embodiment 12.
Embodiment 15～17
230 DEG C of the fusing points making in the PVP that is 60 by K value (BASF AG's product) and above-described embodiment 1Polyester at the upper blending extrusion of two axle extruders (φ 44mm, L/D:52), wherein the addition of PVP accounts for polyesterThe 7wt% of fiber, the Temperature Setting of extruder is 180 DEG C of fusing department 245 kneading parts, extrudes in order. WillThe blend obtaining carries out melt spinning, adds trimethyl phosphate (embodiment 15), methyl in spinning processMethyl orthophosphoric acid (embodiment 16), resorcinol two (pentaerythrite) phosphate (embodiment 17), its additionBe equivalent to the 150ppm of polyester fiber in P elements. Spinning temperature is 255 DEG C, and the speed of spinning is 3000m/min,Obtain as-spun fibre, then as-spun fibre is obtained to polyester fiber by 1.7 times of deep processings. To gained polyester fiberEvaluation result in table 4.
Comparative example 7～8
Choose K value and be 10 and 120 PVP (BASF AG's product), other are with embodiment 12. RelativelyIn example 7, the K value of PVP is 10 o'clock, mixing stable, but because its poor heat resistance causes when the spinning moreFracture of wire. In comparative example 8, the K value of PVP is 120 o'clock, because mixing system viscosity is large, occurs extrusion swelling,Mixing property variation.
Table 4
The result demonstration of embodiment 12～17 in table 4, in the preparation method of polyester fiber of the present invention,It is heat stabilizer that the melt spinning stage is added phosphorus, can obtain equally hygroscopicity parameter Δ MR, tone b value, strongAll good polyester fibers of the long-pending and light fastness of degree of stretching and mixing stability and spinnability.
Claims (10)
1. moisture absorption type polyester fiber, is characterized in that, in this polyester fiber, containing polyester and poly N-ethylene lactams and phosphorus is heat stabilizer, and wherein poly N-ethylene lactams accounts for 3～15wt% of polyester fiber weight, and it disperses footpath is below 200nm; Phosphorus is the content of heat stabilizer accounts for polyester fiber weight 50～500ppm in P element; Described poly N-ethylene lactams is polyvinylpyrrolidone.
2. moisture absorption type polyester fiber according to claim 1, is characterized in that, described polyester is the polyester of 200～240 DEG C of fusing points.
3. moisture absorption type polyester fiber according to claim 1 and 2, is characterized in that, in described polyester fiber, poly N-vinyl lactams accounts for 5～12wt% of polyester fiber weight.
4. moisture absorption type polyester fiber according to claim 1, is characterized in that, the K value of described polyvinylpyrrolidone is 15～90.
5. moisture absorption type polyester fiber according to claim 1, is characterized in that, described phosphorus is that heat stabilizer is the bisphosphate based compound shown in formula 1:
Formula 1
R in formula1、R2Independently of one another for can there is substituent aromatic hydrocarbyl.
6. moisture absorption type polyester fiber according to claim 5, is characterized in that, described phosphorus is that heat stabilizer is two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate or two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate.
7. moisture absorption type polyester fiber according to claim 1, is characterized in that, the hygroscopicity parameter Δ MR of this polyester fiber is more than 1.0%, and tone b value is below 5.0, and light fastness is more than 3 grades.
8. the preparation method of moisture absorption type polyester fiber, is characterized in that, is to carry out blend on two more than 45 axle extruders by polyester and poly N-ethylene lactams at draw ratio L/D, and wherein the addition of poly N-ethylene lactams accounts for 3～15wt% of polyester fiber weight; The blend melt spinning obtaining is obtained to as-spun fibre, this as-spun fibre is further stretched and obtains polyester fiber; Adding in blend stage or melt spinning stage the phosphorus that accounts for polyester fiber weight 50ppm～500ppm in P elements is heat stabilizer; Described poly N-ethylene lactams is polyvinylpyrrolidone.
9. the preparation method of moisture absorption type polyester fiber according to claim 8, is characterized in that, described phosphorus is that heat stabilizer added in the blend stage.
10. the preparation method of moisture absorption type polyester fiber according to claim 8 or claim 9, is characterized in that, described polyester is the polyester of 200～240 DEG C of fusing points, and described spinning temperature is in the scope of 220～270 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201380045855.XA CN104619897B (en) | 2012-10-09 | 2013-10-09 | Moisture absorption type polyester fiber and preparation method thereof |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103790741 | 2012-10-09 | ||
| CN201210379074.1A CN103710781A (en) | 2012-10-09 | 2012-10-09 | Hygroscopic polyester fiber and manufacturing method thereof |
| PCT/CN2013/084901 WO2014056429A1 (en) | 2012-10-09 | 2013-10-09 | Hygroscopic polyester fiber and manufacturing method thereof |
| CN201380045855.XA CN104619897B (en) | 2012-10-09 | 2013-10-09 | Moisture absorption type polyester fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104619897A CN104619897A (en) | 2015-05-13 |
| CN104619897B true CN104619897B (en) | 2016-05-04 |
Family
ID=50404116
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210379074.1A Pending CN103710781A (en) | 2012-10-09 | 2012-10-09 | Hygroscopic polyester fiber and manufacturing method thereof |
| CN201380045855.XA Expired - Fee Related CN104619897B (en) | 2012-10-09 | 2013-10-09 | Moisture absorption type polyester fiber and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210379074.1A Pending CN103710781A (en) | 2012-10-09 | 2012-10-09 | Hygroscopic polyester fiber and manufacturing method thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6296059B2 (en) |
| CN (2) | CN103710781A (en) |
| WO (1) | WO2014056429A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105463614B (en) * | 2014-09-12 | 2020-01-24 | 东丽纤维研究所（中国）有限公司 | Method for producing moisture-absorbing and releasing polyester fiber |
| CN107502990A (en) * | 2017-08-30 | 2017-12-22 | 广州弘雅服装科技有限公司 | A kind of high water absorption moisture absorption polyester fiber, high water absorption Hygroscopic material and preparation and application |
| CN118127662A (en) * | 2024-05-08 | 2024-06-04 | 广东安之伴实业有限公司 | Antibacterial and moisture-absorbing modified polyester fabric as well as preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122494A (en) * | 2011-11-18 | 2013-05-29 | 东丽纤维研究所（中国）有限公司 | Moisture-absorption polyester fiber and manufacturing method thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5167419A (en) * | 1974-12-05 | 1976-06-11 | Toray Industries | KYUSUI KYUSHITSUSEISENI |
| JP3139315B2 (en) * | 1995-01-25 | 2001-02-26 | 東レ株式会社 | Hygroscopic composite fiber using copolyester excellent in hygroscopic property |
| TW317577B (en) * | 1995-01-25 | 1997-10-11 | Toray Industries | |
| JPH09132823A (en) * | 1995-11-06 | 1997-05-20 | Nippon Ester Co Ltd | Polyester conjugate fiber |
| JP3804097B2 (en) * | 1996-03-29 | 2006-08-02 | 東レ株式会社 | Support stockings with excellent wearing comfort |
| JP2000178845A (en) * | 1998-12-10 | 2000-06-27 | Du Pont Toray Co Ltd | Covered elastic yarn and its production |
| JP2002155425A (en) * | 2000-11-15 | 2002-05-31 | Nippon Shokubai Co Ltd | Hygroscopic fiber and method for producing thermoplastic polyester-based resin composition |
| JP2003129340A (en) * | 2001-10-19 | 2003-05-08 | Teijin Ltd | Polyester fiber and method for producing the same |
| CN1258010C (en) * | 2002-03-29 | 2006-05-31 | 东华大学 | Anti-electrostatic nano compound polyester fibre and making method thereof |
| JP4375073B2 (en) * | 2004-03-24 | 2009-12-02 | 東レ株式会社 | Hygroscopic polyester fiber and method for producing the same |
| JP5946255B2 (en) * | 2010-09-17 | 2016-07-06 | 株式会社日本触媒 | N-vinyl lactam polymer and process for producing the same |
| JP5655632B2 (en) * | 2011-02-28 | 2015-01-21 | 東レ株式会社 | Sea-island composite cross-section fiber made of alkali-eluting polyester |
| CN102796352B (en) * | 2011-05-23 | 2016-04-13 | 东丽纤维研究所（中国）有限公司 | A kind of damp absorbent polyester, preparation method and the fiber be made up of it |
| CN102838739B (en) * | 2011-06-22 | 2015-08-05 | 东丽纤维研究所（中国）有限公司 | A kind of Moisture-absorption copolyester and preparation method thereof |
| CN103120375B (en) * | 2011-11-18 | 2016-03-30 | 东丽纤维研究所（中国）有限公司 | A kind of hygroscopicity fabric and uses thereof |
| JP5915273B2 (en) * | 2012-03-08 | 2016-05-18 | 東レ株式会社 | Hygroscopic polyester fiber and method for producing the same |
-
2012
- 2012-10-09 CN CN201210379074.1A patent/CN103710781A/en active Pending
-
2013
- 2013-10-09 JP JP2015534903A patent/JP6296059B2/en not_active Expired - Fee Related
- 2013-10-09 WO PCT/CN2013/084901 patent/WO2014056429A1/en active Application Filing
- 2013-10-09 CN CN201380045855.XA patent/CN104619897B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122494A (en) * | 2011-11-18 | 2013-05-29 | 东丽纤维研究所（中国）有限公司 | Moisture-absorption polyester fiber and manufacturing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "亚磷酸酯类抗氧剂研究进展";纪巍等;《塑料科技》;20080723;第36卷(第6期);第88-93页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015532366A (en) | 2015-11-09 |
| WO2014056429A1 (en) | 2014-04-17 |
| JP6296059B2 (en) | 2018-03-20 |
| CN103710781A (en) | 2014-04-09 |
| CN104619897A (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5589886B2 (en) | Polyalkylene terephthalate resin composition and fiber comprising the same | |
| KR101611321B1 (en) | Fiber for polyester-based artificial hair and headdress product | |
| CN101535371A (en) | Polyether ester elastomer composition | |
| EP3510077A1 (en) | Modified polyester masterbatch for textile applications and manufacturing process thereof | |
| TWI753033B (en) | a polyester | |
| WO2010035591A1 (en) | Polyester polymerization catalyst and method for producing polyester using same | |
| CN104619897B (en) | Moisture absorption type polyester fiber and preparation method thereof | |
| CN110528108A (en) | A kind of preparation method of multicomponent copolyester elastomer | |
| JP4677726B2 (en) | Polyester composition and fibers comprising the same | |
| CN102796352B (en) | A kind of damp absorbent polyester, preparation method and the fiber be made up of it | |
| JP7251260B2 (en) | Cationic dyeable polyester and method for producing the same | |
| CN114846185B (en) | Wet nonwoven fabric and product comprising same | |
| TW200411095A (en) | Poly (trimethylene terephthalate) bicomponent fiber process | |
| CN112981610A (en) | Environment-friendly hydrophilic low-melting-point PET composite short fiber and preparation method thereof | |
| CN101469059A (en) | Preparation of flame-retardant copolymerization modified poly(trimethylene terephthalate) | |
| CN103774269A (en) | Hygroscopic polyester fibre and preparation method and purpose thereof | |
| JP2024501362A (en) | Polyester staple fiber for wet-laid nonwoven fabric, wet-laid nonwoven fabric containing the same, and manufacturing method thereof | |
| CN104099685A (en) | Preparation method for hygroscopic polyester fiber, hygroscopic polyester fiber and application thereof | |
| KR102619704B1 (en) | Heavy metal free-antimicrobial polyester draw textured yarn and Manufacturing method thereof | |
| TW200403276A (en) | Polyester composition and method of manufacturing the same | |
| CN105780188A (en) | Polyester fiber with moisture absorption/desorption performance and preparation method thereof | |
| CN106103540B (en) | Polyester and resin composition and its manufacture method | |
| TWI805829B (en) | Polyester composition | |
| JP2023508484A (en) | Fiber assembly for automobile interior materials and automobile interior materials including the same | |
| KR20230004992A (en) | Polyester draw textured yarn with anti-trouble of skin and Manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160504 Termination date: 20191009 |