CN104684962A - Copolymerized polyester and polyester fiber formed from same - Google Patents
Copolymerized polyester and polyester fiber formed from same Download PDFInfo
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- CN104684962A CN104684962A CN201380049834.5A CN201380049834A CN104684962A CN 104684962 A CN104684962 A CN 104684962A CN 201380049834 A CN201380049834 A CN 201380049834A CN 104684962 A CN104684962 A CN 104684962A
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- polyoxyethylene glycol
- copolyester
- polyethylene terephthalate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
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- General Chemical & Material Sciences (AREA)
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Abstract
The present invention provides: a copolymerized polyester which has high moisture absorption characteristics, while maintaining excellent characteristics of a polyester; and a polyester fiber which is formed from this copolymerized polyester and has excellent moisture absorption. A copolymerized polyester of the present invention is a copolymerized polyester which is obtained by copolymerizing 10-25% by weight of a polyethylene glycol having a number average molecular weight of 8,000-20,000 and comprises ethylene terephthalate as a main repeating unit, and which is characterized by having an amorphous structure that is mainly formed of a polyethylene glycol, while having a polyethylene terephthalate coexistent with the polyethylene glycol.
Description
Technical field
The present invention relates to a kind of trevira that there is hygroscopic copolyester and contain it.More specifically, the present invention relates to a kind of can separately spinning there is excellent hygroscopic copolyester and by containing its trevira of water absorbability excellence.
Background technology
At present, take polyethylene terephthalate as the polyester of representative, due to excellent in intensity, thermostability and chemical proofing etc., so be widely used in the purposes such as fiber, film and formed body.But, because polyethylene terephthalate is essentially hydrophobicity, so pole lacks water absorbability, when using as clothes, produce when humidity height " feeling of oppression and heat ", or producing electrostatic when humidity is low in the winter time, it is desirable material that snugness of fit does not claim.In addition, when using as resin or film etc., also there is the problem of the charged grade due to agent of low hygroscopicity in polyethylene terephthalate.
In order to solve such problem, proposing copolymerization on the side chain of polyester and there is the method for the glycol of oxyalkylene glycol (with reference to patent documentation 1.) and in the polyester copolymerization containing the method for the dicarboxylic acid of metal organic sulfonate (with reference to patent documentation 2.) etc. in the polyester copolymerization there is the method for the compound of hygroscopic property.But, by copolymerization moisture absorbing component can be bulk modified by polyester polymers in the polyester, the problem of the advantage that the polyester that there is the mechanical characteristics losing so-called excellence has originally.
In addition, propose by by acrylic or methacrylic acid graft polymerization in trevira, after graft polymerization, utilize basic metal to replace these carboxyls to give hygroscopic method (with reference to patent documentation 3 further.)。But there are the following problems in this motion: photostabilization reduces, be attached to composition because of moisture absorbing component or fiber sheath causes producing the problem such as stick-slip, the reduction of time dependent intensity, so not yet reach practical.
In addition, giving in hygroscopic method in the post-treatment stage of fiber, when dyeing or in the fiber fabric characteristic of gained, there is various problem.Therefore, in order to give water absorbability in the stage manufacturing fiber and solve aforementioned problems, propose to there is high hygroscopic hygroscopicity resin as core, and the scheme of the sheath-core type conjugate fiber be coated to by the sheath of polyester is (with reference to patent documentation 4 ~ 8.)。But, in these sheath-core type conjugate fiber, when the hot-water cure of refining or dyeing etc., moisture and the significantly swelling of hygroscopicity resin due to core, so there is fiber surface to occur slight crack (sheath is damaged), the cloth and silk quality such as hygroscopicity resin externally flows out, fastness of dyeing worsens significantly reduce such problem.
For the object suppressing this sheath breakage, propose and by the melt-spinning stage, the method for the hollow bulb adjoined with water absorbability core composition is set (with reference to patent documentation 9 and 10 in advance.)。But, under carry out Fibrotic situation with the cross-sectional shape with hollow bulb as this motion, when implementing twisted filament processing or false twisting processing to fiber, in described operation, there is hollow bulb destroy, there is the problem that sheath breakage occurs because hot-water cure subsequently causes absorbent polymer swelling in the same manner as above-mentioned situation.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 48-8270 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2-26985 publication
Patent documentation 3: Japanese Laid-Open Patent Publication 52-74020 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2-99612 publication
Patent documentation 5: Japanese Unexamined Patent Publication 4-361616 publication
Patent documentation 6: Japanese Unexamined Patent Publication 4-341617 publication
Patent documentation 7: Japanese Unexamined Patent Publication 8-198954 publication
Patent documentation 8: Japanese Unexamined Patent Publication 9-132871 publication
Patent documentation 9: Japanese Unexamined Patent Publication 9-111579 publication
Patent documentation 10: Japanese Laid-Open Patent Publication 52-55721 publication
Summary of the invention
Invent problem to be solved
Therefore, the object of the invention is to, a kind of problem overcoming above-mentioned prior art is provided, maintain the characteristic that polyester is originally excellent, and there is the trevira of the copolyester of high moisture-absorption characteristics and the water absorbability excellence containing this copolyester.
For solving the means of problem
The present invention is the invention that will solve the problem, the polyoxyethylene glycol of copolyester of the present invention 10 ~ 25 % by weight number-average molecular weights 8000 ~ 20000 that have been copolymerization, predominant repeat unit is the copolyester of ethylene glycol terephthalate, have main containing polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist.
According to the preferred implementation of copolyester of the present invention, described main containing polyoxyethylene glycol, in non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, the ratio of polyoxyethylene glycol is 70 ~ 99 % by weight.
According to the preferred implementation of copolyester of the present invention, copolyester of the present invention, by DSC (differential scanning calorimeter), 300 DEG C are warming up to the heat-up rate of 16 DEG C/min, keep 5 minutes temperature constant states, then carry out quick refrigeration, be again warming up to 300 DEG C with the heat-up rate of 16 DEG C/min, in the process, the melting peak observed in the scope more than 200 DEG C is present in the scope of 251 ~ 260 DEG C.
According to the preferred implementation of copolyester of the present invention, the moisture absorption parameter △ MR of copolyester of the present invention is 2 ~ 10%.
In the present invention, the trevira of water absorbability excellence can be obtained by described copolyester.
Invention effect
According to the present invention, a kind of copolyester when maintaining the characteristic of polyester script excellence with high moisture-absorption characteristics can be obtained.Copolyester of the present invention, water absorbability is high, and can spinning individually, the cloth etc. that the trevira of gained can be made up of monofilament, well as underwear, Sportswear and wadding etc. conformable material and use.
Embodiment
Copolyester of the present invention be copolymerization 10 ~ 25 % by weight number-average molecular weight 8000 ~ 20000 polyoxyethylene glycol, main repeating unit is the copolyester of ethylene glycol terephthalate.
In the present invention, main repeating unit is that the polyester of ethylene glycol terephthalate refers to, will form derivative and as the ethylene glycol of diol component as the polyester of main component as the terephthalic acid of sour composition and their ester.Preferably in whole diol component, ethylene glycol accounts for more than 80 % by mole, more preferably accounts for the polyester of more than 90 % by mole.In the scope not damaging effect of the present invention, the such as scope of less than 20 % by mole, as the diol component beyond ethylene glycol, also can copolymerization cyclohexanedimethanol, butyleneglycol, neopentyl glycol and Diethylene Glycol etc.
In order to give copolyester water absorbability of the present invention, polyoxyethylene glycol in necessary copolymerization.
For in the present invention as the polyoxyethylene glycol that copolymer composition is used, number-average molecular weight is 8000 ~ 20000 is important.Number-average molecular weight is measured by terminal group quantitative method.Terminal group quantitative method is obtained the method for molecular weight.
For the present invention, in the copolyester be made up of polyoxyethylene glycol and polyethylene terephthalate, find, by making polyoxyethylene glycol be specific number-average molecular weight, to make moisture-absorption characteristics become very big.Specifically, by using number-average molecular weight to be the polyoxyethylene glycol of more than 8000, hygroscopic property becomes very big.Although this reason is not yet clear and definite, can thinks when the number-average molecular weight of polyoxyethylene glycol is more than 8000, make hygroscopic property become high because the polyoxyethylene glycol in polymkeric substance and polyethylene terephthalate form special structure.
In addition, if the number-average molecular weight of polyoxyethylene glycol is more than 20000, then reduce with the reactivity of polyethylene terephthalate, worsen or the polyoxyethylene glycol problem that stripping is so in the hot water so there is throwing.
For the number-average molecular weight of polyoxyethylene glycol, set out from the viewpoint of the formability of copolyester, particularly throwing, be preferably less than 15000, more excellent is less than 10000.
In copolyester of the present invention, the copolymerization ratios of polyoxyethylene glycol is necessary for 10 ~ 25 % by weight.If the copolymerization ratios of polyoxyethylene glycol is less than 10 % by weight, then can not get the water absorbability of copolyester, water absorbability becomes the water absorbability with the polyester equal extent of polyoxyethylene glycol in non-copolymerization.In addition, from melt molding, the viewpoint of such as throwing is set out, and the copolymerization ratios of polyoxyethylene glycol needs to be less than 25 % by weight.If copolymerization ratios is more than 25 % by weight, then there is the tendency that the physical strength of the products formed of the use under not resistant against high temperatures region or gained reduces.In addition, when for the manufacture of fiber, exist and can not use such problem with monofilament.
By making the copolymerization ratios of polyoxyethylene glycol be less than 25 % by weight, spinnability improves, and can accelerate spinning speed, and productivity improves, and can obtain fine denier fiber further.For the copolymerization ratios of polyoxyethylene glycol, be more preferably less than 20 % by weight, more preferably less than 15 % by weight.
When making polyethylene terephthalate and polyoxyethylene glycol copolymerization, except the non-crystal structure formed by polyoxyethylene glycol and the non-crystal structure formed by polyethylene terephthalate, the copolyester of gained also has the non-crystal structure that polyethylene terephthalate and polyoxyethylene glycol coexist.
In addition, in the non-crystal structure that polyethylene terephthalate and polyoxyethylene glycol coexist, be formed main containing polyethylene terephthalate, non-crystal structure that polyethylene terephthalate coexists with polyoxyethylene glycol, and mainly contain polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist.In copolyester of the present invention, in these non-crystal structures, need to have main containing polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist.
In the present invention, due to have main containing polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, thus hygroscopic property uprises, and then the formability such as spinnability also becomes good.
Main containing polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, measure second-order transition temperature by use temperature amplitude modulation differential scanning calorimeter (TM-DSC) and learn.Specifically, following method is utilized to measure.
Copolyester after melting, is fully cooled at the temperature of 290 DEG C in the water of the temperature of 25 DEG C.By dry at 25 DEG C for the copolyester cooled, remove the moisture being attached to surface, obtain working sample.Under temperature range-85 ~ 300 DEG C, heat-up rate 2 DEG C/min, nitrogen environment, use TM-DSC to measure the phase in version behavior of the sample of gained, DSC Signal separator is become reversible composition and irreversible composition.Second-order transition temperature is observed by reversible composition.
If confirm, the second-order transition temperature that measured by TM-DSC is higher than the second-order transition temperature (-67 DEG C) of polyoxyethylene glycol and be less than 0 DEG C, then can confirm to exist main containing polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist.
In addition, in the present invention main containing polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, if the ratio of polyoxyethylene glycol is more than 70 % by weight, then water absorbability is higher, is preferred implementation.The ratio of polyoxyethylene glycol is more preferably more than 80 % by weight.
In addition, in the present invention main containing polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, if polyoxyethylene glycol (PEG) ratio is less than 99 % by weight, then, when for the manufacture of fiber, can use with monofilament.Polyoxyethylene glycol ratio is more preferably less than 90 % by weight.
Main containing polyoxyethylene glycol, the ratio of polyoxyethylene glycol in non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, measure second-order transition temperature (Tg by temperature amplitude modulation differential scanning calorimeter (TM-DSC)
.obs(unit is K)), can be calculated by second-order transition temperature according to the following formula of Couchman (formula 1).
(in formula 1, X
pETfor mainly containing polyoxyethylene glycol, the weight fraction of polyethylene terephthalate in non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, X
pEGfor mainly containing polyoxyethylene glycol, the weight fraction of polyoxyethylene glycol in non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, X
pET=1-X
pEGset up.In addition, △ C
p, PETfor heat capacity difference (the △ C before and after the glass transition of polyethylene terephthalate monomer
p, PET=0.4052Jg
-1k
-1), △ C
p, PEGfor heat capacity difference (the △ C before and after the glass transition of polyalkylene glycol monomer
p, PEG=0.8672Jg
-1k
-1), T
g, PETfor the second-order transition temperature (T of polyethylene terephthalate monomer
g, PET=342K), T
g, PEGrepresent the second-order transition temperature (T of polyalkylene glycol monomer
g, PEG=206K).)。
Because copolyester of the present invention is the high and copolyester of water absorbability excellence of thermotolerance, so carry out melt molding, fiber, film and products formed etc. can be performed well in, particularly can be used as the raw material of synthon well.In this case, in order to have sufficient water absorbability, moisture absorption parameter (△ MR) is preferably more than 2%.Moisture absorption parameter (△ MR) is more preferably more than 4%.In addition, if the moisture absorption parameter of copolyester is less than 10%, then there is spinnability, stretchiness becomes good tendency, is preferred implementation.
Here, moisture absorption parameter (△ MR) refers to, test portion with the standard state damping stabilization of 20 DEG C × 65%R.H. is moved to the high humidity state of 30 DEG C × 90%R.H., the weight gain (g) after 24 hours is divided by the value (%) of adiabatic drying weight (g) gained of test portion.Here, adiabatic drying weight (g) refers to, carries out drying and be dried to the weight of the test portion till not observing changes in weight with the temperature of 105 DEG C.
In copolyester of the present invention, the tensio-active agents such as the pigment such as titanium oxide, carbon black, alkylbenzene sulfonate, antioxidant, anti-tinting material, photostabilizer and static inhibitor etc. can be added within the scope without prejudice to the object of the present invention.
Copolyester of the present invention is manufactured by the polymerization process such as ester-interchange method or esterification process.When ester-interchange method, the ester adding terephthalic acid in reaction vessel forms derivative and ethylene glycol, under the existence of transesterification catalyst, react at the temperature of 150 ~ 250 DEG C, then stablizer and polymerizing catalyst etc. is added, temperature in heated under reduced pressure to 260 ~ 300 of below 500Pa DEG C, reacts 3 ~ 5 hours, can obtain copolyester thus.
In addition, when esterification process, terephthalic acid and ethylene glycol is added in reaction vessel, under nitrogen pressurization, at the temperature of 150 ~ 260 DEG C, carry out esterification, after esterification terminates, add stablizer and polymerizing catalyst etc., temperature in heated under reduced pressure to 260 ~ 300 of below 500Pa DEG C, reacts 3 ~ 5 hours, can obtain copolyester thus.
In the manufacture of copolyester of the present invention, as the interpolation period of polyoxyethylene glycol, can before esterification or transesterification reaction, together add with other raw material, in addition, also add before can starting to polyreaction after esterification or transesterification reaction terminate, but the latter is preferred embodiment.
In the present invention, number-average molecular weight be more than 8000 polyoxyethylene glycol can obtain with the solid state such as thin slice or powder.When adding polyoxyethylene glycol, the temperature being heated to more than 70 DEG C is added with the state of melting, before the decompression of polycondensation reaction starts, make it disperse fully, polyoxyethylene glycol becomes easily and polyethylene terephthalate reacts thus, the copolyester of gained can have main containing polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, hygroscopic property uprises.
In addition, even if because the copolyester of gained also can improve spinnability, can accelerate spinning speed when independent fiber type, improve productivity, fine denier fiber can be obtained further, so be preferred embodiment.
As transesterification catalyst used during manufacture copolyester of the present invention, zinc acetate, manganous acetate, magnesium acetate and four titanium butoxide etc. can be enumerated.In addition, as catalyst for polymerization, ANTIMONY TRIOXIDE SB 203 99.8 PCT, germanium dioxide etc. can be enumerated.
Copolyester of the present invention, specifically obtains by following method.
By the oligopolymer of the bis-β-hydroxyethyl terephthalate by esterification gained (hereinafter sometimes referred to BHT.) cooling, make solid state, then pulverize, obtain pulverous BHT.Pulverous BHT and pulverous polyoxyethylene glycol are fully mixed, then they is added in polycondensation reaction device, stir the temperature melting with 250 ~ 270 DEG C.Add stablizer and polymerizing catalyst etc. in BHT to melting and the mixture of polyoxyethylene glycol, the temperature in heated under reduced pressure to 260 ~ 300 of below 500Pa DEG C, reacts 3 ~ 5 hours, can obtain copolyester thus.
In addition, after using transesterification reaction device or esterification device synthesis BHT, when BHT being transferred to polycondensation reaction device from these reaction units by transfer tube, by injecting the polyoxyethylene glycol of melting in the midway of transfer tube, and stir immediately in polycondensation reaction device, polyoxyethylene glycol differential is fallen apart.Then, add stablizer and polymerizing catalyst etc. in the BHT in melting and the mixture of polyoxyethylene glycol, the temperature in heated under reduced pressure to 260 ~ 300 of below 500Pa DEG C, reacts 3 ~ 5 hours, can obtain copolyester thus.In this process, strainer is set in transfer tube, if injected polyoxyethylene glycol before BHT is about to by strainer, then easily makes polyoxyethylene glycol be dispersed in BHT by the strainer of transfer tube midway.
Copolyester of the present invention can use the forming methods such as extrusion moulding, blow molding, vacuum forming and injection molding to make various synthetic resin.Especially, if utilize melt-spinning by copolymerization of polyester fiber, then hygroscopic property easily plays, and is preferred embodiment.
As the fiber employing copolyester of the present invention, 20 ~ 100 % by weight of preferred formed fabric integer is copolyester of the present invention.When copolyester of the present invention lower than 20 % by weight, almost do not observe the effect that moisture absorption dehumidification is improved.In addition, from the view point of sufficient moisture absorption dehumidification, 50 ~ 100 % by weight of preferred all fibers are made up of copolyester of the present invention.
Especially, be made up of copolyester of the present invention by fabric integer (100%), namely form in fact independent fiber type, the water absorbability of fiber can be played to greatest extent.
In addition, in existing sheath-core type conjugate fiber, there is the problem that the swelling caused because of moisture absorption causes that sheath breaks etc., but by using the fiber containing copolyester of the present invention with the form of independent silk, also can address these problems.In addition, by using containing the fiber of copolyester of the present invention with the form of independent silk, because copolyester exposes on surface, so have the effect that rate of moisture absorption accelerates.
The water absorbability of the fiber containing copolyester of the present invention is important standard in the comfortableness of the clothes when determining heat.When being made dress material, in order to give comfortableness, moisture absorption parameter (△ MR) is preferably more than 2.0%.In addition, from the view point of comfortableness, moisture absorption parameter (△ MR) is more preferably more than 4.0%.But, if the water absorbability parameter of the fiber containing copolyester is more than 20%, then sometimes the characteristic of fiber is impacted.Such as, intensity reduction sometimes, photostabilization worsen and become large, become and are unsuitable in middle uses such as dress material purposes.Moisture absorption parameter is more preferably less than 10%.
The filament number of the fiber containing copolyester of the present invention, from the view point of being suitable for needing hygroscopic dress material purposes, is preferably below 10dtex.Filament number is more preferably below 5dtex.In addition, in the present invention, the fiber of thinner filament number can be obtained, also can obtain the fiber of below 1dtex.
Fiber containing copolyester of the present invention manufactures by melt-spinning operation.Specifically, copolyester of the present invention is heated to 280 ~ 300 DEG C temperature and from spinning nozzle melting discharge.From spinning nozzle discharge strand usually after spinning through cooling and batching.
In addition, as spinning speed, by being set to 500m/ minute ~ 10000m/ minute, can molecular orientation be produced, the operation property passed through can be improved in follow-up stretching process.
In addition, the manufacturing process of the fiber of the copolyester containing invention also can adopt first temporarily batches spun strand, re-uses the method that drawing machine stretches to this strand; Or temporarily do not batch spun strand but carry out the techniques such as the direct spinning stretching mode of spin-drawing operation continuously
Embodiment
A. moisture absorption parameter (△ MR):
Prepare the mensuration test portion of 3g, measure its adiabatic drying weight (Wd).This test portion is become in damping in the constant temperature and humidity machine (エ ス ペ ッ Network LHU-123) of the state of 20 DEG C × 65%R.H. and place 24 hours, measure the test portion weight (W20) becoming equilibrium state, then, the setting of constant temperature and humidity machine is changed to 30 DEG C × 90%R.H., measure the weight (W30) of placing further after 24 hours, obtain moisture absorption parameter according to following formula I.
Moisture absorption parameter (△ MR)=(W30-W20)/Wd (%) formula I
B. second-order transition temperature, PEG ratio:
Use temperature amplitude modulation differential scanning calorimeter (TM-DSC), in a nitrogen environment, is warming up to the temperature of 300 DEG C from-85 DEG C with the speed of 2 DEG C/min, obtain the second-order transition temperature of less than 0 DEG C observed at reversible composition.
Device: TA Instruments DSC Q1000
Data parsing: TA Instruments ユ ニ バ ー サ Le ア Na リ シ ス 2000
In addition, by the second-order transition temperature of gained, following (formula 1) is utilized to calculate PEG ratio.
(in formula 1, X
pETfor mainly containing polyoxyethylene glycol, the weight fraction of polyethylene terephthalate in non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, X
pEGfor mainly containing polyoxyethylene glycol, the weight fraction of polyoxyethylene glycol in non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, X
pET=1-X
pEGset up.In addition, △ C
p, PETfor heat capacity difference (the △ C before and after the glass transition of polyethylene terephthalate monomer
p, PET=0.4052Jg
-1k
-1), △ C
p, PEGfor heat capacity difference (the △ C before and after the glass transition of polyalkylene glycol monomer
p, PEG=0.8672Jg
-1k
-1), T
g, PETfor the second-order transition temperature (T of polyethylene terephthalate monomer
g, PET=342K), T
g, PEGrepresent the second-order transition temperature (T of polyalkylene glycol monomer
g, PEG=206K).)。
C. spinnability:
Vacuum-drying 10 hours at the temperature of 150 DEG C, under the condition of spinning temperature 290 DEG C, spinning speed 1000m/ minute, spinning nozzle bore 0.23 μm of-12H (hole), fracture of wire frequency when carrying out 1kg spinning with following benchmarking exercise.Fracture of wire is not all evaluated as zero, confirmation had fracture of wire but less and not hindering the ranging assessments of operability to be △, being evaluated as often there is fracture of wire ×.It is qualified zero and △ to be considered as.
D. stretchiness:
Fracture of wire frequency when the undrawn yarn obtained by spinning being stretched with the condition of draft temperature 80 DEG C, stretching ratio 2.7 times with following benchmarking exercise.Fracture of wire is not all evaluated as zero, confirmation had fracture of wire but less and not hindering the ranging assessments of operability to be △, being evaluated as often there is fracture of wire ×.It is qualified zero and △ to be considered as.
E. melting peak
By DSC (differential scanning calorimeter), be warming up to 300 DEG C with heat-up rate 16 DEG C/min, after keeping 5 minutes temperature constant states, carry out quick refrigeration, again be warming up to 300 DEG C with heat-up rate 16 DEG C/min, in the process, using found endotherm(ic)peak as melting peak.
(embodiment 1)
In the transesterification reaction device of the reaction unit that transesterification reaction device and polycondensation reaction device are linked up with the transfer tube being provided with 400 object strainers, add the manganous acetate as transesterification catalyst of the dimethyl terephthalate (DMT) of 429g and the ethylene glycol of 274g and 0.1g, while heat up in a steamer methyl alcohol at the temperature of 140 ~ 240 DEG C, carry out transesterification reaction, then, add the trimethyl phosphite 99 of 0.15g wherein, thus synthesis BHT.Then, when BHT being transferred to polycondensation reaction device from transesterification reaction device by transfer tube, the polyoxyethylene glycol 75g of the molecular weight 8300 (Sanyo changes into the PEG6000 of industrial society) of the temperature and melting that are heated to 70 DEG C is injected by the transfer tube before strainer, starts to stir while transfer terminates.Then, the Irganox1010 as antioxidant (BASF society system) of 0.1g, the polysiloxane as defoamer of 0.1g and the ANTIMONY TRIOXIDE SB 203 99.8 PCT as polymerizing catalyst of 0.15g is added in polycondensation reaction device, under the decompression of 100Pa, under the condition of 290 DEG C of temperature, carry out polymerization in 3 hours.Then, the copolyester of gained is discharged in cold water with line strand, carries out pelletizing immediately and obtain polyester granulate.
In the multipolymer obtained like this, the ratio of the polyoxyethylene glycol of institute's copolymerization is 15 % by weight.In addition, the △ MR of the copolyester of gained is 3.2%, and second-order transition temperature (Tg) is-59 DEG C and 90 DEG C.Using the Tg of the Tg of low temperature side as the many non-crystal structure of polyoxyethylene glycol, calculate the ratio of polyoxyethylene glycol, result, the ratio of polyoxyethylene glycol is 89%.
Then, by the copolyester particle of gained with the Temperature Vacuum of 150 DEG C dry 10 hours, under the condition of spinning temperature 290 DEG C, output 32g/ minute, spinning speed 1000m/ minute, spinning nozzle bore 0.23 μm of-24H (hole), carry out melt-spinning.Spinnability well and do not observe fracture of wire.Then, stretch under the condition of draft temperature 80 DEG C, stretching ratio 3.3 times.When stretching, there is not the winding of fracture of wire or monofilament, also good in stretchiness.
Total fiber number containing the fiber of rewarding copolyester is 97dtex (filament number 4dtex), △ MR is 4.0%, is the fiber of water absorbability excellence.
(embodiment 2 ~ 4, comparative example 1 ~ 2)
Change to except the value shown in table 1 except by the copolymerization ratios of PEG, implement in mode similarly to Example 1.Result illustrates in Table 1.
Copolymerization ratios as embodiment 2 ~ 4, PEG can obtain bibulous trevira when being in scope of the present invention.But, the copolymerization ratios as comparative example 1 ~ 2, PEG be scope of the present invention outer time moisture-absorption characteristics low or when spinning or stretch and often fracture of wire occurs, the trevira desired by failing to obtain.
(embodiment 5 ~ 6, comparative example 3 ~ 4)
Change to except the value shown in table 2 except by the molecular weight of PEG, implement in mode similarly to Example 1.Result is illustrated in table 2.
(comparative example 5)
Except not injecting polyoxyethylene glycol from transfer tube but being added directly to except polycondensation reaction device with powdery, carry out in mode similarly to Example 1.Result illustrates in table 2.
As embodiment 6, when the molecular weight of PEG is 20000, in stretchiness, confirms there is fracture of wire a little, but be the degree of no problem in operability.But as comparative example 4, when the molecular weight of PEG is 100000, fiber generation fibrillation, spinnability and stretchiness worsen.This can not carry out copolyreaction due to the molecular weight of PEG up to 100000, PEG but form blended state.
As embodiment 5, when the molecular weight of PEG is 10000, the equal no problem of spinnability, stretchiness.
In addition, as comparative example 3, when the molecular weight of PEG is 3200, there are fracture of wire, spinnability poor and stretchiness is also poor.
In addition, as comparative example 5, when adding PEG with powdery, second-order transition temperature be-67 DEG C, and in that mainly contain polyoxyethylene glycol, that polyoxyethylene glycol and polyethylene terephthalate coexist non-crystal structure, the ratio of PEG is 100%.That is, not the non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, but the non-crystal structure that polyoxyethylene glycol is independent.In addition, gained polymer system spinnability difference and can not fiber be obtained.
Claims (5)
1. a copolyester, its be copolymerization 10 ~ 25 % by weight number-average molecular weight be the polyoxyethylene glycol of 8000 ~ 20000, predominant repeat unit is the copolyester of ethylene glycol terephthalate, it is characterized in that, have main containing polyoxyethylene glycol, non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist.
2. copolyester according to claim 1, is characterized in that, main containing polyoxyethylene glycol, in non-crystal structure that polyoxyethylene glycol and polyethylene terephthalate coexist, the ratio of polyoxyethylene glycol is 70 ~ 99 % by weight.
3. copolyester according to claim 1 and 2, it is characterized in that, 300 DEG C are warming up to the heat-up rate of 16 DEG C/min with DSC and differential scanning calorimeter, keep 5 minutes temperature constant states, then quick refrigeration is carried out, again be warming up to 300 DEG C with the heat-up rate of 16 DEG C/min, in this process, the melting peak observed in the scope more than 200 DEG C is present in the scope of 251 ~ 260 DEG C.
4. the copolyester according to any one of claims 1 to 3, is characterized in that, moisture absorption parameter Δ MR is 2 ~ 10%.
5. a trevira, it comprises the copolyester according to any one of Claims 1 to 4.
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| JP2012-212031 | 2012-09-26 | ||
| JP2012212031 | 2012-09-26 | ||
| PCT/JP2013/075118 WO2014050652A1 (en) | 2012-09-26 | 2013-09-18 | Copolymerized polyester and polyester fiber formed from same |
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| CN104684962A true CN104684962A (en) | 2015-06-03 |
| CN104684962B CN104684962B (en) | 2016-12-28 |
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| KR (1) | KR102079522B1 (en) |
| CN (1) | CN104684962B (en) |
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| CN109440473A (en) * | 2018-10-29 | 2019-03-08 | 东莞宝丽美化工有限公司 | A kind of preparation method of the fluffy soft finishing agent of non-silicon electrostatic resistance hydrophile |
| US20210325325A1 (en) * | 2018-08-31 | 2021-10-21 | Bursa Teknik Universitesi | A quantitative analysis method for fiber compositions |
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| KR102250972B1 (en) * | 2014-03-25 | 2021-05-12 | 도레이 카부시키가이샤 | Fiber having phase separation structure and manufacturing method for such fiber |
| KR101673343B1 (en) | 2015-05-06 | 2016-11-07 | 현대자동차 주식회사 | Coupled torsion beam axle of vehicles |
| CN111655919A (en) * | 2018-01-25 | 2020-09-11 | 东丽株式会社 | Spun-bonded non-woven fabric |
| JP7059850B2 (en) * | 2018-07-26 | 2022-04-26 | 東レ株式会社 | Laminated non-woven fabric |
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| WO2014050652A1 (en) | 2014-04-03 |
| KR20150063351A (en) | 2015-06-09 |
| JP6090308B2 (en) | 2017-03-08 |
| CN104684962B (en) | 2016-12-28 |
| MY164820A (en) | 2018-01-30 |
| JPWO2014050652A1 (en) | 2016-08-22 |
| TW201420633A (en) | 2014-06-01 |
| KR102079522B1 (en) | 2020-02-20 |
| TWI607034B (en) | 2017-12-01 |
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