CN104684962B - Copolyester and comprise its polyester fiber - Google Patents
Copolyester and comprise its polyester fiber Download PDFInfo
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- CN104684962B CN104684962B CN201380049834.5A CN201380049834A CN104684962B CN 104684962 B CN104684962 B CN 104684962B CN 201380049834 A CN201380049834 A CN 201380049834A CN 104684962 B CN104684962 B CN 104684962B
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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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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention provides a kind of characteristic maintaining polyester excellence and the copolyester with high moisture-absorption characteristics and the polyester fiber of the hygroscopicity excellence containing this copolyester.The Polyethylene Glycol that number-average molecular weight is 8000～20000 of the copolyester of the present invention 10～25 weight % that have been combined polymerization, predominant repeat unit be the copolyester of ethylene glycol terephthalate, it is characterized in that there is non crystalline structure that mainly contain Polyethylene Glycol, that Polyethylene Glycol coexists with polyethylene terephthalate.
Description
Technical field
The present invention relates to a kind of polyester fiber that there is hygroscopic copolyester and contain it.More specifically, the present invention
Relate to a kind of can individually spinning there is excellent hygroscopic copolyester and by the excellent polyester fiber of the hygroscopicity containing it.
Background technology
At present, the polyester with polyethylene terephthalate as representative, due at intensity, heat stability and chemically-resistant medicine
The aspects such as moral character are excellent, so being widely used in the purposes such as fiber, film and molded body.But, due to poly terephthalic acid second
Diol ester is essentially hydrophobicity, so pole lacks hygroscopicity, in the case of using as clothes, produces when humidity height "
Feeling of oppression and heat ", or humidity produces electrostatic time low in the winter time, and not claiming on snugness of fit is preferable material.It addition, it is poly-to benzene
Naphthalate, when using as resin or film etc., there is also the problem of charged grade due to agent of low hygroscopicity.
In order to solve such problem, it is proposed that on the side chain of polyester, copolymerization has the side of the glycol of oxyalkylene glycol
Method is (with reference to patent documentation 1.) and the method for the copolymerization dicarboxylic acids containing metal organic sulfonate in the polyester (with reference to patent documentation 2.) etc.
Copolymerization has the method for compound of moisture pick-up properties in the polyester.But, can be by polyester by copolymerization moisture absorbing component in the polyester
Polymer is bulk modified, exists and loses the problem that the polyester of so-called excellent mechanical property has the advantage that originally.
It addition, propose by by acrylic or methacrylic acid glycerol polymerization in polyester fiber, poly-in grafting further
Alkali metal is utilized to replace these carboxyls to give hygroscopic method (with reference to patent documentation 3 after conjunction.).But, this motion exists
Following problem: light resistance reduces, be attached to compositions because of moisture absorbing component or fiber sheath results in stick-slip, time dependent intensity fall
The problem such as low, so not yet reaching practical.
Additionally, give in hygroscopic method in the post-treatment stage of fiber, when dyeing or the fiber fabric of gained is special
There is various problem in property aspect.Therefore, in order to give hygroscopicity in the stage manufacturing fiber and solve aforementioned problems, it is proposed that with
There is high hygroscopic hygroscopicity resin as core, and the scheme (ginseng of the sheath-core type conjugate fiber being coated to by the sheath of polyester
According to patent documentation 4～8.).But, in these sheath-core type conjugate fiber, when the hot water treatment of refined or dyeing etc., due to
The hygroscopicity resin of core is aqueous and significantly swelling, so there is fiber surface slight crack (sheath is damaged) occurs, hygroscopicity resin to
The cloth and silk quality such as outside outflow, colorfastness significantly deterioration reduce such problem.
For the purpose that this sheath of suppression is damaged, it is proposed that arranged by the melt spinning stage in advance and adjoin with hygroscopicity core composition
The method of hollow bulb (with reference to patent documentation 9 and 10.).But, as this motion to have the cross sectional shape of hollow bulb
Carry out Fibrotic in the case of, to fiber implement twisted filament processing or false twisting processing in the case of, in described operation occur in
Sky portion destroys, and causes absorbent polymer swelling that sheath breakage occurs with above-mentioned situation similarly, the presence of because of hot water treatment subsequently
Problem.
Prior art literature
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, it is an object of the invention to, it is provided that a kind of problem overcoming above-mentioned prior art, maintain polyester the most excellent
Characteristic, and there is the copolyester of high moisture-absorption characteristics and the polyester fiber that hygroscopicity containing this copolyester is excellent.
For solving the means of problem
The present invention is to solve the invention of the problems referred to above, the copolyester of the present invention has been copolymerization 10～25 weight % numbers are equal
The Polyethylene Glycol of molecular weight 8000～20000, predominant repeat unit be the copolyester of ethylene glycol terephthalate, have
Non crystalline structure that mainly contain Polyethylene Glycol, that Polyethylene Glycol coexists with polyethylene terephthalate.
The preferred implementation of the copolyester according to the present invention, described in mainly contain Polyethylene Glycol, Polyethylene Glycol with
In the non crystalline structure that polyethylene terephthalate coexists, the ratio of Polyethylene Glycol is 70～99 weight %.
The preferred implementation of the copolyester according to the present invention, the copolyester of the present invention, by DSC (differential scanning
Calorimeter), it is warming up to 300 DEG C with the programming rate of 16 DEG C/min, keeps 5 minutes temperature constant states, then carry out quick refrigeration,
Again being warming up to 300 DEG C with the programming rate of 16 DEG C/min, in the process, that observes in the scope more than 200 DEG C is molten
Xie Feng is present in the scope of 251～260 DEG C.
The preferred implementation of the copolyester according to the present invention, the moisture absorption parameter △ MR of the copolyester of the present invention is 2
～10%.
In the present invention, can be obtained, by described copolyester, the polyester fiber that hygroscopicity is excellent.
Invention effect
According to the present invention, in the case of a kind of characteristic the most excellent at maintenance polyester can be obtained, there is high moisture-absorption characteristics
Copolyester.The copolyester of the present invention, hygroscopicity is high, and can spinning individually, the polyester fiber of gained can be by monofilament
The fabric etc. made, is work perfectly well as the conformable material of underwear, gym suit and wadding etc. and uses.
Detailed description of the invention
The Polyethylene Glycol of the number-average molecular weight 8000～20000 of the copolyester of the present invention 10～25 weight % that have been copolymerization
, the main copolyester that repetitive is ethylene glycol terephthalate.
In the present invention, main repetitive is that the polyester of ethylene glycol terephthalate refers to, using as acid composition
P-phthalic acid and their ester form derivant and as the ethylene glycol of diol component as the polyester of main component.Preferably
All in diol component, ethylene glycol accounts for 80 moles of more than %, more preferably accounts for the polyester of 90 moles of more than %.Do not damaging the present invention
In the range of effect, the such as scope of 20 moles of below %, as the diol component beyond ethylene glycol, it is also possible to copolymerization hexamethylene
Dimethanol, butanediol, neopentyl glycol and diethylene glycol etc..
In order to give the copolyester hygroscopicity of the present invention, it is necessary to Polyethylene Glycol in copolymerization.
For in the present invention as the Polyethylene Glycol used by copolymer composition, number-average molecular weight is 8000～20000 to be important
's.Number-average molecular weight is measured by terminal groups quantitative method.Terminal groups quantitative method be by the integration ratio of the terminal groups of NMR and main chain and
The method obtaining molecular weight.
For the present invention, in the copolyester being made up of Polyethylene Glycol and polyethylene terephthalate, find logical
Crossing and making Polyethylene Glycol is specific number-average molecular weight, makes moisture-absorption characteristics become very big.Specifically, by using number-average molecular weight
Being the Polyethylene Glycol of more than 8000, moisture pick-up properties becomes very big.Although this reason is not yet clear and definite, but it is believed that at Polyethylene Glycol
When number-average molecular weight is more than 8000, owing to the Polyethylene Glycol in polymer and polyethylene terephthalate are formed special
Structure and make moisture pick-up properties become high.
If it addition, the number-average molecular weight of Polyethylene Glycol is more than 20000, then with the reactivity of polyethylene terephthalate
Reduce, so occurring throwing to deteriorate or the such problem of Polyethylene Glycol dissolution in the hot water.
For the number-average molecular weight of Polyethylene Glycol, from the viewpoint of the mouldability of copolyester, particularly throwing, excellent
Electing less than 15000 as, more excellent is less than 10000.
In the copolyester of the present invention, the copolymerization ratios of Polyethylene Glycol is necessary for 10～25 weight %.If being total to of Polyethylene Glycol
Poly-ratio is less than 10 weight %, then can not get the hygroscopicity of copolyester, and hygroscopicity becomes and Polyethylene Glycol poly-in non-copolymerization
The hygroscopicity of ester equal extent.It addition, from melt molding, such as from the viewpoint of throwing, the copolymerization ratios of Polyethylene Glycol
Needing is below 25 weight %.If copolymerization ratios is more than 25 weight %, then there is the use or gained not being resistant under high-temperature area
Products formed mechanical strength reduce tendency.It addition, when being used for manufacturing fiber, exist and can not use such asking with monofilament
Topic.
By making the copolymerization ratios of Polyethylene Glycol be below 25 weight %, spinnability improves, it is possible to accelerate spinning speed, raw
Product improves, and can obtain fine denier fiber further.For the copolymerization ratios of Polyethylene Glycol, below more preferably 20 weight %,
More preferably below 15 weight %.
In the case of making polyethylene terephthalate and Polyethylene Glycol copolymerization, except the amorphous formed by Polyethylene Glycol
Outside structure and the non crystalline structure that formed by polyethylene terephthalate, the copolyester of gained also has poly-terephthaldehyde
The non crystalline structure that acid glycol ester coexists with Polyethylene Glycol.
It addition, in the non crystalline structure that polyethylene terephthalate and Polyethylene Glycol coexist, be formed and mainly contain
Polyethylene terephthalate, non crystalline structure that polyethylene terephthalate coexists with Polyethylene Glycol, and mainly contain
Non crystalline structure that have Polyethylene Glycol, that Polyethylene Glycol coexists with polyethylene terephthalate.Copolyester in the present invention
In, in these non crystalline structures, need to have and mainly contain Polyethylene Glycol, Polyethylene Glycol and polyethylene terephthalate altogether
The non crystalline structure deposited.
In the present invention, mainly contain Polyethylene Glycol, Polyethylene Glycol with polyethylene terephthalate altogether owing to having
The non crystalline structure deposited, thus moisture pick-up properties uprises, and then the mouldability such as spinnability also becomes good.
Non crystalline structure that mainly contain Polyethylene Glycol, that Polyethylene Glycol coexists with polyethylene terephthalate, can lead to
Cross use temperature amplitude modulation differential scanning calorimeter (TM-DSC) to measure glass transition temperature and learn.Specifically, utilize
Following method is measured.
After copolyester is melted at a temperature of 290 DEG C, sufficiently cool in the water of the temperature of 25 DEG C.By cooled down
Copolyester is dried at 25 DEG C, removes the moisture being attached to surface, it is thus achieved that measure sample.Temperature range-85～300 DEG C,
Under programming rate 2 DEG C/min, nitrogen environment, use the phase in version behavior of the sample of TM-DSC mensuration gained, DSC signal is divided
From becoming reversible composition and irreversible composition.Glass transition temperature can be observed by reversible composition.
If the glass transition temperature that confirmation is measured by TM-DSC is than the glass transition temperature (-67 DEG C) of Polyethylene Glycol
High and be less than 0 DEG C, then can confirm that to exist and mainly contain Polyethylene Glycol, Polyethylene Glycol and polyethylene terephthalate
The non crystalline structure that ester coexists.
It addition, in the present invention mainly contain Polyethylene Glycol, Polyethylene Glycol coexists with polyethylene terephthalate
Non crystalline structure, if the ratio of Polyethylene Glycol is more than 70 weight %, then hygroscopicity is higher, for preferred implementation.Poly-second two
The ratio of alcohol is more preferably more than 80 weight %.
It addition, in the present invention mainly contain Polyethylene Glycol, Polyethylene Glycol coexists with polyethylene terephthalate
Non crystalline structure, if Polyethylene Glycol (PEG) ratio is below 99 weight %, then when being used for manufacturing fiber, it is possible to make with monofilament
With.Polyethylene Glycol ratio is more preferably below 90 weight %.
Poly-second in non crystalline structure that mainly contain Polyethylene Glycol, that Polyethylene Glycol and polyethylene terephthalate coexist
The ratio of glycol, measures glass transition temperature (Tg by temperature amplitude modulation differential scanning calorimeter (TM-DSC).obs(unit
For K)), can calculate by glass transition temperature according to the following formula (formula 1) of Couchman.
(in formula 1, XPETNon-with what polyethylene terephthalate coexisted for mainly containing Polyethylene Glycol, Polyethylene Glycol
The weight fraction of polyethylene terephthalate, X in crystal structurePEGRight with poly-for mainly containing Polyethylene Glycol, Polyethylene Glycol
The weight fraction of Polyethylene Glycol, X in the non crystalline structure that PET coexistsPET=1-XPEGSet up.It addition, △ CP, PET
For heat capacity difference (the △ C before and after the glass transition of polyethylene terephthalate monomerP, PET=0.4052Jg-1K-1), △
CP, PEGFor heat capacity difference (the △ C before and after the glass transition of polyalkylene glycol monomerP, PEG=0.8672Jg-1K-1), TG, PETIt is poly-
Glass transition temperature (the T of ethylene glycol terephthalate monomerG, PET=342K), TG, PEGRepresent the glass of polyalkylene glycol monomer
Glass transition temperature (TG, PEG=206K).).
Owing to the copolyester of the present invention is the copolyester that thermostability is high and hygroscopicity is excellent, so being melt into
Type, can perform well in fiber, thin film and products formed etc., particularly can function well as the raw material of synthetic fibers.This
In the case of, in order to have sufficient hygroscopicity, moisture absorption parameter (△ MR) is preferably more than 2%.Moisture absorption parameter (△ MR) is more preferably
It is more than 4%.If it addition, the moisture absorption parameter of copolyester is less than 10%, then having spinnability, draftability to become good inclining
To, it is preferred implementation.
Here, moisture absorption parameter (△ MR) refers to, by the examination with the standard state damping stabilisation of 20 DEG C × 65%R.H.
Material moves to the high humidity state of 30 DEG C × 90%R.H., and the weight gain (g) after 24 hours is divided by the adiabatic drying weight of test portion
The value (%) of (g) gained.Here, adiabatic drying weight (g) refers to, is dried and is dried with the temperature of 105 DEG C to observing not
The weight of the test portion changing to weight.
In the copolyester of the present invention, the face such as titanium oxide, carbon black can be added within the scope without prejudice to the object of the present invention
The surfactants such as material, alkylbenzenesulfonate, antioxidant, stainblocker, photostabilizer and antistatic additive etc..
The copolyester of the present invention is manufactured by the polymerization such as ester-interchange method or esterification process.Situation at ester-interchange method
Under, the ester adding p-phthalic acid in reaction vessel forms derivant and ethylene glycol, in the presence of ester exchange catalyst,
React at a temperature of 150～250 DEG C, then add stabilizer and polymerization catalyst etc., add under the decompression of below 500Pa
Heat, to the temperature of 260～300 DEG C, is reacted 3～5 hours, thus can be obtained copolyester.
It addition, in the case of esterification process, add p-phthalic acid and ethylene glycol in reaction vessel, pressurize at nitrogen
Under, at a temperature of 150～260 DEG C, carry out esterification, after esterification terminates, add stabilizer and polymerization catalyst
Deng, in the temperature of the heated under reduced pressure to 260～300 DEG C of below 500Pa, react 3～5 hours, thus can obtain copolymerization and gather
Ester.
In the manufacture of the copolyester of the present invention, as the interpolation period of Polyethylene Glycol, can be at esterification or ester
Before exchange reaction, together add with other raw material, alternatively, it is also possible to anti-to polymerization after esterification or ester exchange reaction terminate
Should start to add before, but the latter is preferred embodiment.
In the present invention, number-average molecular weight be more than 8000 Polyethylene Glycol can obtain with the solid state such as thin slice or powder
Take.When adding Polyethylene Glycol, the temperature being heated to more than 70 DEG C is added with melted state, and the decompression in polycondensation reaction is opened
Making it disperse fully before beginning, thus Polyethylene Glycol becomes easily to react with polyethylene terephthalate, gained
Copolyester can have amorphous knot that mainly contain Polyethylene Glycol, that Polyethylene Glycol coexists with polyethylene terephthalate
Structure, moisture pick-up properties uprises.
Even if it addition, because the copolyester of gained also is able to improve spinnability, can add in the case of independent fiber type
Speed spinning speed, improving productivity, can obtaining fine denier fiber further, so being preferred embodiment.
As ester exchange catalyst used when manufacturing the copolyester of the present invention, zinc acetate, manganese acetate, acetic acid can be enumerated
Magnesium and four titanium butoxide etc..It addition, as catalyst for polymerization, antimony trioxide, germanium dioxide etc. can be enumerated.
The copolyester of the present invention, specifically can be obtained by following method.
By oligomer (the hereinafter sometimes referred to BHT of the bis-β-hydroxyethyl terephthalate by esterification gained.) cold
But, make solid state, then pulverize, it is thus achieved that the BHT of powder.By BHT and the Polyethylene Glycol of powder of powder
It is sufficiently mixed, then adds them into polycondensation reaction device, stir and melt with the temperature of 250～270 DEG C
Melt.Stabilizer and polymerization catalyst etc., subtracting at below 500Pa is added in the BHT the melted mixture with Polyethylene Glycol
Pressure is heated to the temperature of 260～300 DEG C, reacts 3～5 hours, thus can obtain copolyester.
It addition, use ester exchange reaction device or esterification device synthesis BHT after, by transfer tube by BHT from this
When a little reaction units are transferred to polycondensation reaction device, by injecting melted Polyethylene Glycol in the midway of transfer tube, and poly-
Condensation reaction device stirs immediately, makes Polyethylene Glycol differential dissipate.Then, at the mixture of the BHT melted Yu Polyethylene Glycol
Middle interpolation is by stabilizer and polymerization catalyst etc., in the temperature of the heated under reduced pressure to 260～300 DEG C of below 500Pa, reacts 3
～5 hours, thus can obtain copolyester.During this, transfer tube arranges filter, if will pass through at BHT
Inject Polyethylene Glycol before filter, then easily make Polyethylene Glycol be dispersed in BHT by the filter of transfer tube midway.
The copolyester of the present invention can use the molding sides such as extrusion molding, blow molding, vacuum forming and injection moulding
Method makes various synthetic resin.Especially, if utilizing melt spinning by copolymerization of polyester fiber, then moisture pick-up properties is easily sent out
Wave, be preferred embodiment.
As the fiber of the copolyester employing the present invention, 20～100 weight % that the fiber preferably constituted is overall
Copolyester for the present invention.In the case of the copolyester of the present invention is less than 20 weight %, it is barely perceivable and makes moisture absorption
The effect that dehumidification improves.It addition, from the viewpoint of sufficient moisture absorption dehumidification, 50～100 weights of preferably all fibers
Amount % is made up of the copolyester of the present invention.
Especially, it is made up of the copolyester of the present invention by fiber overall (100%), i.e. essentially forms independent type fine
Dimension, can play the hygroscopicity of fiber to greatest extent.
It addition, in existing sheath-core type conjugate fiber, have what the swelling caused because of moisture absorption caused that sheath ruptured etc.
Problem, but by using the fiber of the copolyester containing the present invention with the form of independent silk, it is also possible to solve these problems.This
Outward, by using the fiber of the copolyester containing the present invention, owing to copolyester exposes, institute on surface with the form of independent silk
To have the effect that rate of moisture absorption accelerates.
The hygroscopicity of the fiber of the copolyester containing the present invention, determine heat time clothes comfortableness in terms of be weight
The standard wanted.When being made dress material, in order to be able to give comfortableness, moisture absorption parameter (△ MR) is preferably more than 2.0%.Additionally, from
From the viewpoint of comfortableness, moisture absorption parameter (△ MR) more preferably more than 4.0%.But, if the fiber containing copolyester
The characteristic of fiber, more than 20%, is impacted by hygroscopicity parameter the most sometimes.Such as, intensity reduces sometimes, light resistance deteriorates and becomes
Greatly, become unsuitable in middle uses such as dress material purposes.Moisture absorption parameter is more preferably less than 10%.
The filament number of the fiber of the copolyester containing the present invention, from being suitable to need the viewpoint of hygroscopic dress material purposes
Set out, preferably below 10dtex.Filament number is more preferably below 5dtex.It addition, in the present invention, it is possible to obtain thinner
The fiber of filament number, it is also possible to obtain the fiber of below 1dtex.
The fiber of the copolyester containing the present invention can be manufactured by melt spinning operation.Specifically, by the present invention's
Copolyester is heated to temperature the melted discharge from spinning head of 280～300 DEG C.The strand discharged from spinning head is generally spinning
Through cooling down and batching after going out.
It addition, as spinning speed, by being set to 500m/ minute～10000m/ minute, molecularly oriented can be produced,
Follow-up stretching process can improve the operation property passed through.
It addition, the manufacturing process of the fiber containing the copolyester invented can also use first temporarily batches spun silk
Bar, re-uses the method that this strand is stretched by stretching-machine；Or the most temporarily batch spun strand but be carried out continuously spinning
The techniques such as the direct spinning stretching mode of stretching process
Embodiment
A. moisture absorption parameter (△ MR):
Prepare the mensuration test portion of 3g, measure its adiabatic drying weight (Wd).This test portion is become 20 DEG C × 65% in damping
The constant temperature and humidity machine (エ ス ペ ッ Network LHU-123) of state R.H. is placed 24 hours, measures the test portion becoming poised state
Weight (W20), then, is changed to the setting of constant temperature and humidity machine 30 DEG C × 90%R.H., measures after placing 24 hours further
Weight (W30), obtain moisture absorption parameter according to following formula I.
Moisture absorption parameter (△ MR)=(W30-W20)/Wd (%) formula I
B. glass transition temperature, PEG ratio:
Use temperature amplitude modulation differential scanning calorimeter (TM-DSC), in a nitrogen environment, with the speed of 2 DEG C/min from-85
DEG C it is warming up to the temperature of 300 DEG C, obtains the glass transition temperature of less than 0 DEG C observed at reversible composition.
Device: TA Instruments DSC Q1000
Data parsing: TA Instruments ユ ニ バ サ Le ア Na リ シ ス 2000
It addition, by the glass transition temperature of gained, utilize following (formula 1) to calculate PEG ratio.
(in formula 1, XPETNon-with what polyethylene terephthalate coexisted for mainly containing Polyethylene Glycol, Polyethylene Glycol
The weight fraction of the polyethylene terephthalate in crystal structure, XPEGFor mainly containing Polyethylene Glycol, Polyethylene Glycol with poly-
The weight fraction of the Polyethylene Glycol in the non crystalline structure that ethylene glycol terephthalate coexists, XPET=1-XPEGSet up.It addition, △
CP, PETFor heat capacity difference (the △ C before and after the glass transition of polyethylene terephthalate monomerP, PET=0.4052Jg-1K-1), △ CP, PEGFor heat capacity difference (the △ C before and after the glass transition of polyalkylene glycol monomerP, PEG=0.8672Jg-1K-1), TG, PET
Glass transition temperature (T for polyethylene terephthalate monomerG, PET=342K), TG, PEGRepresent polyalkylene glycol monomer
Glass transition temperature (TG, PEG=206K).).
C. spinnability:
It is vacuum dried 10 hours at a temperature of 150 DEG C, at spinning temperature 290 DEG C, spinning speed 1000m/ minute, spray webbing
Under conditions of draught animals footpath 0.23 μm-12H (hole), carry out fracture of wire frequency during 1kg spinning with following benchmarking exercise.By a fracture of wire
The most it is not evaluated as zero, will confirm that fracture of wire but less and be △ at the ranging assessments not hindering operability, will usually occur fracture of wire
Be evaluated as ×.It is qualified to be considered as zero and △.
D. draftability:
With the following benchmarking exercise undrawn yarn to being obtained by spinning with draft temperature 80 DEG C, stretching ratio 2.7 times
Condition fracture of wire frequency when stretching.Fracture of wire is not the most evaluated as zero, will confirm that fracture of wire but less and do not hinder
The ranging assessments of operability is △, will usually occur fracture of wire is evaluated as ×.It is qualified to be considered as zero and △.
E. melting peak
By DSC (differential scanning calorimetry (DSC)), it is warming up to 300 DEG C with programming rate 16 DEG C/min, keeps 5 minutes constant temperature
After state, carry out quick refrigeration, be again warming up to 300 DEG C with programming rate 16 DEG C/min, in the process, by found
Endothermic peak is as melting peak.
(embodiment 1)
Ester exchange reaction device and the polycondensation reaction device transfer tube of the filter being provided with 400 mesh are being linked
In the ester exchange reaction device of the reaction unit come, add the dimethyl terephthalate (DMT) of 429g and the ethylene glycol of 274g and
The manganese acetate as ester exchange catalyst of 0.1g, evaporates methanol, while carrying out ester friendship at a temperature of 140～240 DEG C
Change reaction, then, be added to the trimethyl phosphate of 0.15g, thus synthesize BHT.Then, by transfer tube by BHT from
When ester exchange reaction device is transferred to polycondensation reaction device, will warm up the temperature of 70 DEG C and melted molecular weight 8300 (three
Foreignize into the PEG6000 of industry society) Polyethylene Glycol 75g inject by the transfer tube before filter, terminate in transfer
Start simultaneously at stirring.Then, in polycondensation reaction device, add the Irganox1010 (BASF as antioxidant of 0.1g
Society's system), the polysiloxanes as defoamer of 0.1g and the antimony trioxide as polymerization catalyst of 0.15g, 100Pa's
Under decompression, under conditions of 290 DEG C of temperature, carry out polymerization in 3 hours.Then, the copolyester of gained is discharged to cold with strands shape
In water, carry out pelletizing immediately and obtain polyester granulate.
In the copolymer so obtained, the ratio of the Polyethylene Glycol of institute's copolymerization is 15 weight %.It addition, the copolymerization of gained gathers
The △ MR of ester is 3.2%, and glass transition temperature (Tg) is-59 DEG C and 90 DEG C.The Tg of low temperature side is many as Polyethylene Glycol
The Tg of non crystalline structure, calculates the ratio of Polyethylene Glycol as a result, the ratio of Polyethylene Glycol is 89%.
Then, the copolyester granule of gained is dried 10 hours with the Temperature Vacuum of 150 DEG C, spinning temperature 290 DEG C,
Melted spinning is carried out under conditions of 32g/ minute output, spinning speed 1000m/ minute, spinning head bore 0.23 μm-24H (hole)
Silk.Spinnability well and does not observes fracture of wire.Then, draw under conditions of draft temperature 80 DEG C, stretching ratio 3.3 times
Stretch.When stretching, there is not the winding of fracture of wire or monofilament, the best in terms of draftability.
The total fiber number of the fiber containing rewarding copolyester is 97dtex (filament number 4dtex), and △ MR is 4.0%,
For the fiber that hygroscopicity is excellent.
(embodiment 2～4, comparative example 1～2)
In addition to the copolymerization ratios of PEG is changed to the value shown in table 1, implement in the way of similarly to Example 1.Result
Illustrate in Table 1.
Such as embodiment 2～4, the copolymerization ratios of PEG is obtained in that bibulous polyester is fine when being in the scope of the present invention
Dimension.But, such as comparative example 1～2, the copolymerization ratios of PEG be the scope of the present invention outer time moisture-absorption characteristics low or when spinning or draw
Stretch and fracture of wire occurs often, fail to obtain desired polyester fiber.
(embodiment 5～6, comparative example 3～4)
In addition to the molecular weight of PEG is changed to the value shown in table 2, implement in the way of similarly to Example 1.By result
Illustrate in table 2.
(comparative example 5)
Except not injecting Polyethylene Glycol but in addition to being added directly to polycondensation reaction device with powdery from transfer tube, with
The same mode of embodiment 1 is carried out.Result illustrates in table 2.
Such as embodiment 6, when the molecular weight of PEG is 20000, in terms of draftability, confirm somewhat to have fracture of wire, but for grasping
The degree of no problem in the property made.But, such as comparative example 4, when the molecular weight of PEG is 100000, fiber generation fibrillation, spinning
Property and draftability deteriorate.This is owing to the molecular weight of PEG is up to 100000, and PEG can not carry out copolyreaction but be formed and be blended
State.
Such as embodiment 5, when the molecular weight of PEG is 10000, the equal no problem of spinnability, draftability.
It addition, such as comparative example 3, when the molecular weight of PEG is 3200, has fracture of wire, spinnability poor and draftability be the poorest.
It addition, such as comparative example 5, in the case of adding PEG with powdery, glass transition temperature is-67 DEG C, mainly contains poly-
In ethylene glycol, non crystalline structure that Polyethylene Glycol and polyethylene terephthalate coexist, the ratio of PEG is 100%.I.e., not
It is Polyethylene Glycol and non crystalline structure that polyethylene terephthalate coexists, but the non crystalline structure that Polyethylene Glycol is independent.This
Outward, gained polymer system spinnability difference and fiber can not be obtained.
Claims (5)
1. a copolyester, the poly-second two that number-average molecular weight is 8000～20000 of its 10～25 weight % that have been combined polymerization
Alcohol, predominant repeat unit be the copolyester of ethylene glycol terephthalate, it is characterised in that have and mainly contain poly-second two
Alcohol, non crystalline structure that Polyethylene Glycol coexists with polyethylene terephthalate,
Polyethylene Glycol in non crystalline structure that mainly contain Polyethylene Glycol, that Polyethylene Glycol and polyethylene terephthalate coexist
Ratio be 70～99 weight %.
Copolyester the most according to claim 1, it is characterised in that with DSC i.e. differential scanning calorimetry (DSC) with 16 DEG C/min
Programming rate be warming up to 300 DEG C, keep 5 minutes temperature constant states, then carry out quick refrigeration, again with the liter of 16 DEG C/min
Temperature speed is warming up to 300 DEG C, and during this, the melting peak observed in the scope more than 200 DEG C is present in 251～260 DEG C
Scope.
Copolyester the most according to claim 1 and 2, it is characterised in that the combined polymerization poly-second two of 15～25 weight %
Alcohol.
Copolyester the most according to claim 1 and 2, it is characterised in that moisture absorption parameter, Δ MR is 2～10%.
5. a polyester fiber, it comprises the copolyester according to any one of Claims 1 to 4.
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| JP2012212031 | 2012-09-26 | ||
| JP2012-212031 | 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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| CN104684962B true CN104684962B (en) | 2016-12-28 |
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| JP (1) | JP6090308B2 (en) |
| KR (1) | KR102079522B1 (en) |
| CN (1) | CN104684962B (en) |
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| CN106164349B (en) * | 2014-03-25 | 2019-04-23 | 东丽株式会社 | Fiber and its manufacturing method with phase separation structure |
| KR101673343B1 (en) | 2015-05-06 | 2016-11-07 | 현대자동차 주식회사 | Coupled torsion beam axle of vehicles |
| SG11202006937PA (en) * | 2018-01-25 | 2020-08-28 | Toray Industries | Spunbonded nonwoven fabric |
| JP7059850B2 (en) * | 2018-07-26 | 2022-04-26 | 東レ株式会社 | Laminated non-woven fabric |
| TR201812422A2 (en) * | 2018-08-31 | 2018-09-21 | Bursa Teknik Ueniversitesi | A QUANTITATIVE ANALYSIS METHOD FOR FIBER MIXTURES |
| 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 |
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| CN102041578A (en) * | 2010-11-16 | 2011-05-04 | 远纺工业(上海)有限公司 | Modified polyester filiform texture matter capable of extending by absorbing moisture |
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| TWI607034B (en) | 2017-12-01 |
| JP6090308B2 (en) | 2017-03-08 |
| KR20150063351A (en) | 2015-06-09 |
| CN104684962A (en) | 2015-06-03 |
| TW201420633A (en) | 2014-06-01 |
| JPWO2014050652A1 (en) | 2016-08-22 |
| WO2014050652A1 (en) | 2014-04-03 |
| KR102079522B1 (en) | 2020-02-20 |
| MY164820A (en) | 2018-01-30 |
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