CN110484992A - Melt anisotropy aromatic polyester fiber and its manufacturing method - Google Patents
Melt anisotropy aromatic polyester fiber and its manufacturing method Download PDFInfo
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- CN110484992A CN110484992A CN201910762745.4A CN201910762745A CN110484992A CN 110484992 A CN110484992 A CN 110484992A CN 201910762745 A CN201910762745 A CN 201910762745A CN 110484992 A CN110484992 A CN 110484992A
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- aromatic polyester
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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
- D01F6/58—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
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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
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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Abstract
The present invention provides a kind of melting anisotropy aromatic polyester fiber of high-quality that the rear process passability that fibrillation and single wire fracture etc. does not occur with thin filament number and in warp and heat treatment procedure is excellent.The melting anisotropy aromatic polyester fiber is characterized in that: showing that the filament number that anisotropic aromatic polyester is formed is 4.0dtex composite filament below when it is by melting, the villus number in 1,000,000 m of filament length is less than 3.The preferred total fiber number of the aromatic polyester fiber is for 10dtex or more, 500dtex hereinafter, number of monofilaments is in the range of 3~1000.
Description
This case isOn March 31st, 2015, application No. is201580011621.2(PCT/JP2015/ 060292), it is entitledMelt anisotropy aromatic polyester fiber and its manufacturing methodPatent application divisional application.
Technical field
The present invention relates to the fiber fines formed by melting anisotropy aromatic polyester (filament number be 4.0dtex with
Under composite filament).
Background technique
Melting anisotropy aromatic polyester is the polymer that is formed of strand by rigidity, can be in melt spinning
Keep strand height-oriented along fiber axis direction.Additionally, it is known that since melting anisotropy aromatic polyester is with solid state
Polymerization reaction is carried out, solid phase occurs and being heat-treated at high temperature to the fiber after spinning, is spun using melting
Highest intensity, elasticity modulus can be become in the fiber that silk obtains.Due to these characteristics, currently, melting anisotropy fragrance
Adoption ester fiber be used in the yarn fabric of silk-screen printing, coarse cloth, various electric products line reinforcement material, protecting hand
The tension element of bag, the reinforcement material of plastics, optical fiber.In addition, in recent years, due to low-k and low-dielectric loss angle tangent
Such high frequency characteristics and excellent in dimensional stability have been expected to for printed circuit board base fabric.In addition, recently, along with
Mobile phone and PC, the miniaturization of tablet computer, slimming, it is contemplated that arriving the melting thinner to total fiber number, filament number
The demand of anisotropy aromatic polyester fiber.
However, height-oriented melting anisotropy aromatic polyester fiber is since extension at break degree is low, the drawing after spinning
It stretches and is nearly impossible.Therefore, in order to make filament number attenuate, target filament number must be become in the stage of spinning.Make
For the manufacturing method of the thin melting anisotropy aromatic polyester fiber of filament number, for example, propose in patent document 1 with
Under method: will be answered as sea component, to melt anisotropy aromatic polyester as the fabric of island-in-sea type of island component using water-dispersible polyester
Condensating fiber is rolled into cheese, carries out dissolution process to sea component in water in the form of its cheese, thus obtaining filament number is
0.05~1.0dtex and be heat-treated after intensity be 20cN/dtex or more melting anisotropy aromatic polyester fiber.
In addition, the manufacturing method of melting anisotropy aromatic polyester superfine fibre is proposed in patent document 2, it is special
Sign is: sprayed from the nozzle of diameter 0.1mm pore below can be formed the aromatic polyesters of anisotropy melting behaviors into
In row spinning and the melt spinning method wound, condition below (1)~(7) are used.
(1) using+20 DEG C of fusing point of the shear velocity 1000sec in melting anisotropy aromatic polyester-1When melting
Viscosity is less than the polymer of 500Poise；(2) shear velocity when passing through nozzle is set as 103~109sec-1；(3) by nozzle
Ejection linear velocity be set as 40m/ minutes 5m/ minutes or more or less；(4) winding speed is set as 150m/ minutes or more 8000m/
Minute or less；(5) the opposite ratio for spraying linear velocity of winding speed is set as 20 or more；(6) spinneret temperature is set as fusing point+15
DEG C or more；(7) by after ejection apart from nozzle face 30cm the temperature of fiber when is set as Tm-150 DEG C or less.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-216052 bulletin
Patent document 2: Japanese Unexamined Patent Publication 6-166909 bulletin
Summary of the invention
Problems to be solved by the invention
However, in the method for patent document 1, by islands-in-sea bicomponent fibre warp at cheese after, in water at dissolution
Reason is required, therefore easy zbility later becomes difficult.In addition, it is deadlocked between monofilament can be caused when being heat-treated, because
This makes a quality variation due to the single wire fracture and fibrillation in later unwinding.
In contrast, in the method for patent document 2, it is steady to the fiber of thin filament number to can use common spinning head
Surely fiber in carrying out spinning, there is the advantage that cost is cheap, but carry out warp etc. it is unwinding when, easily cause because often
Fibrillation, single wire fracture and fracture of wire caused by the intensity decline of 1 monofilament, the poor quality of obtained fiber.
It is an object of the invention to: the melting of high-quality a kind of thin and fibrillation and single wire fracture not occurring etc. is provided
Anisotropy aromatic polyester fiber.
The method used for solving the problem
The present inventor studies intensively, as a result, it has been found that the present invention.That is, the purpose of the present invention by provide it is a kind of melting it is each to
Anisotropic aromatic polyester fiber and reach, which is characterized in that: when it is by melting
Show that the filament number that anisotropic aromatic polyester is formed is 4.0dtex composite filament below, the suede in 1,000,000 m of filament length
Approximate number is less than 3.The preferred total fiber number of the aromatic polyester fiber is for 10dtex or more, 500dtex hereinafter, number of monofilaments is 3~1000
In the range of.In addition, the present invention also provides a kind of method for manufacturing above-mentioned melting anisotropy aromatic polyester fiber, this method
Show that anisotropic aromatic polyester carries out melt spinning when to melting, obtaining filament number is that 4.0dtex is below compound
Silk, in the method, using in+30 DEG C of fusing point, shear velocity 1000sec-1When melt viscosity be 10Poise or more,
Spinning winding tension is set as 5cN or more, 60cN or less by 50Poise aromatic polyester below.
Invention effect
Although melting anisotropy aromatic polyester fiber filament number of the invention is 4.0dtex hereinafter, but it is one
The fiber of the excellent high-quality of rear process passability of single wire fracture and fibrillation kind does not occur.
Detailed description of the invention
Fig. 1 is the explanatory diagram for indicating the outline of an example of melt spinning device used in the present invention.
Specific embodiment
Hereinafter, the present invention is described in detail.
Aromatic polyester in the present invention shows anisotropic aromatic polyester when being melting.It is shown when the so-called melting
Show that anisotropic aromatic polyester refers to the aromatic polyester with aftermentioned property, that is, inclined being present in 90 ° of orthogonal 2 piece
It, can within the temperature range of can flow when placing polyester sample powder on the heating sample platform between tabula rasa and being heated up
With the property through light.It is by Japanese Patent Publication 56-18016 bulletin and Japanese Patent Publication as such aromatic polyester
Aromatic dicarboxylic acid shown in 55-20008 bulletin etc., aromatic diol and/or aromatic hydroxy-carboxylic and they
The aromatic polyester that derivative is formed, according to circumstances, also include above compound and alicyclic dicarboxylic acid, cycloaliphatic diols,
The copolymer of aliphatic dihydroxy alcohol and their derivative.Wherein, as aromatic dicarboxylic acid, terephthaldehyde can be enumerated
Bis- (4- carboxyphenoxy) ethane of acid, M-phthalic acid, 4,4 '-dicarboxylate biphenyls, 2,6- dicarboxyl naphthalene, 1,2- etc. and general
The hydrogen of these aromatic rings utilizes the compound after alkyl, aryl, alkoxy, halogen substitution.It, can be with as aromatic diol
Enumerate hydroquinone, resorcinol, 4,4 '-dihydroxybiphenyls, 4,4 '-dihydroxy benaophenonels, 4,4 '-dihydroxy hexichol
Bis- (4- hydroxy phenyl) propane of methane, 4,4 '-dihydroxy diphenylethanes, 2,2-, 4,4 '-dihydroxy diphenyl ethers, 4,4 '-
Dihydroxydiphenylsulisomer, 4,4 '-dihydroxy diphenyl sulfides, 2,6- dihydroxy naphthlene, 1,5- dihydroxy naphthlene etc. and by these fragrance
The hydrogen of ring utilizes the compound after alkyl, aryl, alkoxy, halogen substitution.As aromatic hydroxy-carboxylic, can enumerate to hydroxyl
Yl benzoic acid, m-hydroxybenzoic acid, 2 hydroxy naphthalene -6- carboxylic acid, 1- hydroxyl naphthalene -5- carboxylic acid etc. and by these aromatic rings
Hydrogen using alkyl, aryl, alkoxy, halogen replace after compound.As alicyclic dicarboxylic acid, anti-form-1 can be enumerated,
4- dicarboxyl butylcyclohexane, cis- -1,4- dicarboxyl butylcyclohexane etc. and by the hydrogen of these aromatic rings utilize alkyl, aryl, alkane
Compound after oxygroup, halogen substitution.As alicyclic and aliphatic dihydroxy alcohol, anti-form-1,4- dihydroxy basic ring can be enumerated
Hexane, cis- -1,4- dihydroxy butylcyclohexane, ethylene glycol, 14- butanediol, xyxylene glycol etc..
In these combinations, as preferred aromatic polyester in the present invention, for example, can enumerate (1) includes to hydroxyl
40~70 moles of % of yl benzoic acid residue and/or 2 hydroxy naphthalene -6- carboxylic acid residues, above-mentioned aromatic dicarboxylic acid residue 15~
The copolyesters of 15~30 moles of % of 30 moles of % and aromatic diol residue；(2) by terephthalic acid (TPA) and/or M-phthalic acid
The copolyesters formed with Adurol, phenyl hydroquinone and/or hydroquinone；(3) residual comprising P-hydroxybenzoic acid
The copolyesters etc. of 20~80 moles of % of 20~80 moles of % of base and 2 hydroxy naphthalene -6- carboxylic acid residues.
When obtaining aromatic polyester used in the present invention using these raw material, rouge is can be used as it is or utilized
The esterification of fat race or aromatic monocarboxylate or their derivative, aliphatic alcohol or phenols or their derivative etc. carries out polycondensation
Reaction., can be using known bulk polymerization, polymerisation in solution, suspended polymerization etc. as polycondensation reaction, obtained polymer can be with
As former state be used as spinning sample, or can also using powder shaped in inactive gas or decompression under be heat-treated after as spinning
Silk uses sample.It is used afterwards alternatively, being first granulated using extruder progress.
It, can also be in ingredient in the range of the physical property for not reducing melting anisotropy aromatic polyester fiber substantially
Include other polymer or additive (pigment, carbon, heat stabilizer, ultraviolet absorbing agent, lubricant, fluorescent whitening agent
Deng).
In aromatic polyester of the invention, there are the molecular weight ranges suitable for spinning." flow starting temperature " is used to make
For physics value corresponding with the molecular weight of the melt spinning condition is suitable for.About " flow starting temperature ", made using Shimadzu
Made flow tester CFT-500, using the nozzle of diameter 1mm, length 10mm, in pressure 100kg/cm2In the state of,
It is heated up with 4 DEG C/min to aromatic polyester sample, so that sample is passed through Flow in Nozzle and give the table of 4,800 pascal seconds
Viscosity is seen, temperature at this time is defined as " flow starting temperature ".
" flow starting temperature " about melting anisotropy aromatic polyester of the invention is suitably for 290~330 DEG C.
The filament number of melting anisotropy aromatic polyester fiber of the invention is 4.0dtex hereinafter, preferably
2.5dtex is hereinafter, more preferably 1.0dtex or less.Total fiber number ranges preferably from 10dtex or more, 500dtex hereinafter, more
Add preferably 15dtex or more, 450dtex hereinafter, further preferably 20dtex or more, 400dtex or less.The model of number of monofilaments
Enclose preferably 3~1000, more preferably 10~800, further preferably 20~600.
About the melting anisotropy aromatic polyester suitable for melt spinning of the invention, in+30 DEG C of fusing point, shear velocity
1000sec-1When melt viscosity be 10Poise or more, 50Poise or less.As long as in the range, being adapted to stablize manufacture list
Silk size is 4.0dtex aromatic polyester fiber below.That is, being squeezed when melt viscosity is less than 10Poise from spinning head
Polymer out easily becomes drops, and there are the insufficient tendencies of the stability of spinning.When melt viscosity is more than 50Poise, by
It is reduced in draging a property, has the danger for attenuating and occurring single wire fracture along with fiber number, there are the insufficient tendencies of the stability of spinning.
In addition, using capillary rheometer (CAPILOGRAPH) (Toyo Seiki makes made pattern 1B), being utilized about melt viscosity
The nozzle of diameter 0.5mm, length 5mm heat up to aromatic polyester sample with+30 DEG C of fusing point, when sample passes through nozzle,
Apply 1000sec-1Shear velocity, viscosity at this time is defined as melt viscosity.
Aromatic polyester fiber of the invention is manufactured by using melt spinning device for example as shown in Figure 1.In Fig. 1
In, 1 is spinneret, and 2 be spinning packet, and 3 be spinning head, and 4 be heater, and 5 be heat-preservation cylinder.
In melt spinning, well known method is can be used in the melting extrusion about aromatic polyester.In order to be suitable for melting
Spinning is usually granulated aromatic polyester, uses the extruder of extruder type.The resin of extrusion is sent to spinning by piping
Silk head 1, is measured using metering device well known to gear pump etc. (not shown), by entering after filter in spinning packet 2
Spinning head 3.The temperature being piped from polymer to spinning head 3 is set as the fusing point of aromatic polyester or more, below thermal decomposition temperature
It is suitable.
By the heater of setting directly below 4 and heat-preservation cylinder 5 in spinning head 3, the diameter of the fiber sprayed can be made steady
Fixedization, and the surface temperature of the spinning head as caused by external gas and the change of the atmosphere temperature below spinning head can be inhibited
Change, makes to become using the refinement of air-flow uniformly, there is no silk fracture and villus etc., exist and easily become inclining for stable spinning
To.
In addition, the shear velocity in spinneret hole is set as 104~105sec-1It is suitable.This hair is found out using following formula
The shear velocity γ of bright middle meaning.
γ=4Q/ π r3
(wherein, r is the radius (cm) of spinneret hole, and Q is the polymer spray volume (cm of each single hole3/sec))
When within the above range, the orientation of fiber can become sufficiently, to exist and be easy to get the thin fiber of fiber number and be easy
To the tendency of target properties.
In addition, the case where for aromatic polyester fiber, be tired due to carrying out stretching in the rear process after spinning winding
Difficult, therefore filament number is 4.0dtex composite filament below in order to obtain, it is suitable for spraying resin using pore as much as possible
's.Therefore, the aperture (diameter) of spinning head is preferably 0.2mm hereinafter, more preferably 0.18mm or less.
As described above, being utilized after giving defined finish to the aromatic polyester fiber after spinning using feeding means 6
First godet 7 and the second godet 8 are pulled, on reel 9 (spinning reel).Winding speed is preferably 400m/ minutes
Above, 2000m/ minutes hereinafter, further preferably 600m/ minutes or more, 1800m/ minutes or less.The second godet 8 with
The spinning winding tension measured between spinning reel 9 is preferably 5cN or more, 60cN hereinafter, more preferably 10cN or more, 50cN
Hereinafter, further preferably 20cN or more, 40cN or less.When tension is less than 5cN, a twisting cohesion can be made in seal wire because of fiber relaxation
On roller 8, cause the shape defect of reel 9.In warp process later, the reel of shape defect has occurred because wire falling etc. is easy
Fracture of wire and single wire fracture occurs, makes productivity and quality decline.In general, as long as filament number is more than the fiber of 4.0dtex, i.e.,
Make spinning winding tension in 70~100cN or so, the shape of spinning reel will not deform and can be with stable roll around but if single
Silk size hereinafter, when spinning winding tension is more than 60cN, will cause the silk in spinning to be broken and anti-later in 4.0dtex
Single wire fracture, fibrillation in volume process, make productivity and quality decline.In addition, in the present invention, spinning winding tension indicates
The value that the tension applied when winding on reel 9 is measured.
When manufacturing aromatic polyester fiber of the invention, it is weight that spinning winding tension, which is set as 5cN or more, 60cN or less,
It wants.Existing aromatic polyester fiber is based on the industrial materials purposes such as rope and hawser, and total fiber number is thick, and filament number also surpasses
4.0dtex is crossed, the intensity of usual every monofilament is in 20cN or more.When filament number becomes 4.0dtex or less, every monofilament it is strong
Degree will be lower, even the damage of a little also easily causes fibrillation, single wire fracture and fracture of wire.In addition, aromatic polyester
For fiber compared with general polyester fiber, elongation is extremely low, therefore cannot absorb the tension being applied on fiber, also becomes fibril
The reason of change and fracture of wire.In addition, the volume density of spinning reel will be got higher when filament number becomes 4.0dtex or less.This
When, since the monofilament of overlapping is easy to fall into each other, when the fiber to spinning reel carries out unwinding, that this dry Wataru of monofilament, thus
Cause fibrillation and single wire fracture etc..Therefore, in the present invention, winding tension is set as 5cN or more, 60cN when spinning hereinafter,
The load being applied on silk when mitigating spinning winding as much as possible, strongly reduces the volume density of spinning reel, mitigates monofilament
It falls into, prevents fibrillation, single wire fracture and fracture of wire, thus make to melt anisotropy aromatic polyester fiber as high-quality.
For the melting anisotropy aromatic polyester fiber obtained using above-mentioned manufacturing method, even filament number
Single wire fracture and fibrillation will not occur, later in aftermentioned warp and heat treatment for 4.0dtex fine fibre below
Process passability it is also excellent, be a kind of fiber of high-quality.
Carrying out the intensity of fiber obtained from melt spinning to above-mentioned melting anisotropy aromatic polyester is preferably
3.0cN/dtex or more, more preferably 5.0cN/dtex or more.In addition, elongation is preferably 0.5% or more, more preferably
1.0% or more.In addition, elasticity modulus is preferably 300cN/dtex or more, more preferably 400cN/dtex or more.
The melting anisotropy aromatic polyester fiber obtained using spinning can be used as it is, and can also pass through heat treatment
Further high intensity, high resiliency.In this case, before heat treatment, preferably by the fiber of spinning reel temporarily to it
Its heat treatment is with reel warp at packet.At this point, as described above, by the way that the spinning winding tension in spinning process is set as 5cN
Above, 60cN hereinafter, can make the easy zbility of the fiber in warp become well, do not occurred single wire fracture and silk fracture
The silk of high-quality.In heat treated reel warp, in order to equably carry out solid phase, the volume density of packet is preferably
0.01g/cc or more, 1.0g/cc are hereinafter, more preferably 0.8g/cc or less.Wherein, so-called volume density is from outer by what is wrapped
The possessive volume Vf (cc) for the fiber that the outside dimension of size and the heat treatment reel as core material the is found out and quality Wf of fiber
(g), the value calculated using Wf/Vf.In addition, possessive volume Vf is the volume surveyed to the outer dimension of packet, and assume warp
Cylinder is rotational symmetry, the value found out by calculating, and Wf is the value calculated by fiber number and spooling length or utilizes winding front and back
Actual measurement of poor quality value.In order to make volume density be lower, preferably warp speed is set as 500m/ minutes hereinafter, more preferably
It is 400m/ minutes or less.
It is suitable for carrying out heat treatment with the fusing point temperature below of above-mentioned melting anisotropy aromatic polyester fiber.By
This, can carry out the solid phase of aromatic polyester fiber, improve intensity, elasticity modulus.In addition, there are fibres in heat treatment
It is easy the tendency of fusion, therefore interfibrous fusion in order to prevent between dimension, periodically rises to fusing point temperature below from room temperature
Degree is suitable.
For the solid phase in being steadily heat-treated, preferably it is heat-treated under inactive gas atmosphere.But
It is that from the aspect of cost, using dry air, preferably dehumidifying arrives -40 DEG C of dew point or less in advance.That is, such as
There are moisture when fruit solid phase, induce hydrolysis sometimes, cannot fully improve intensity.
Fiber after heat treatment can also as former state provide packet as product, but in order to improve product handling efficiency, preferably
Warp is on paper tube etc. again.In warp after heat treatment, the upper limit of warp speed is not particularly limited, but from mitigate pair
From the aspect of the damage of fiber, preferably 500m/ minutes hereinafter, more preferably 400m/ minutes or less.
As described above, by heat treatment can further production efficiency highland stably obtain it is high-intensitive, high elastic modulus,
Quality also high melting anisotropy aromatic polyester fiber.The intensity of fiber obtained from being heat-treated as described above is preferred
For 10.0cN/dtex or more, more preferably 12.0cN/dtex or more, further preferably 20.0cN/dtex or more.In addition,
Elongation is preferably 1.0% or more, and more preferably 2.0% or more.In addition, elasticity modulus is preferably 400cN/dtex or more,
More preferably 500cN/dtex or more.
Melting anisotropy aromatic polyester fiber of the invention is villus number in 1,000,000 m of filament length less than 3, is weaving
The fiber for the high-quality that there is no problem in process Deng after.More preferred villus number is further preferably no larger than 1 less than 2.It can use
Manufacturing method documented by above-mentioned obtains such fiber.
Embodiment
The present invention is specifically explained hereinafter, enumerating embodiment.Embodiment and comparative example use the melt spinning of Fig. 1
Device carries out the spinning of aromatic polyester fiber.In addition, the present invention is not limited to embodiments discussed below.In embodiment
It is each evaluation carry out as follows.
1) tension test (intensity, elongation, elasticity modulus)
According to JISL 1013 (2010) standard when test, use the cupping machine AGS- of Shimadzu Seisakusho Ltd.
500NX finds out rupture strength elongation and elasticity modulus (initial stage tension with specimen length 200mm, tensile speed 200mm/ minutes
Intensity), it is indicated with the average value of 10 points.
2) spinning winding tension
Using the electronic type tensometer CM-100R of Jin Jinggong machine Co. Ltd. system, in spinning winding, to the second of Fig. 1
Running tension between godet 8 and reel 9 carries out 3 measurements, is indicated with its average value.
3) spinning operability is evaluated
Spinning operability when below to spinning in progress 2 hours or more is evaluated.
Zero silk fracture does not occur, can steadily carry out spinning.
The fracture of the silk within 5 times has occurred in △ in spinning in 2 hours.
× multiple silk fracture occurs, it cannot wind.
4) spinning precursor warp is evaluated
It evaluates below by operability of the fiber warp after 50000m spinning when on iron reel.
Zero single wire fracture and silk fracture do not occur, can steadily carry out warp.
Single wire fracture and silk fracture has occurred in △.
× multiple silk fracture occurs, it is unable to warp to the end.
5) heat treatment silk warp evaluation
Operability of the fiber warp after 50000m is heat-treated when on product paper tube is evaluated below.
Zero single wire fracture and silk fracture do not occur, can steadily carry out warp.
Single wire fracture has occurred in △.
× multiple silk fracture occurs, it is unable to warp to the end.
6) villus number is evaluated
Device F9-AN type is found using springtime electrical (Co., Ltd.) system, villus, and 1,000,000 m are measured to the fiber after heat treatment
Filament length, measurement result is evaluated as described below.
Zero villus number is less than 1
△ villus number 1 or more, less than 3
× villus number 3 or more
7) guide rail operation test
Make the ceramic rod guide rail contact of fiber Yu diameter 4mm with 60 ° of contact angle, and in 300m/min, tension 120g/cm2
Under conditions of run the heat treatment silk of 10,000 m, from the accumulating amount of the attachment on guide rail as described below to process passability into
Row evaluation.
Zero accumulating amount is less than 1mg
△ accumulating amount is 1mg or more, is less than 3mg
× accumulating amount is 3mg or more
[embodiment 1]
Melt anisotropic aromatic polyester as display, using by 40 moles of acetoxy-benzoic acid, to benzene two
Aromatic polyester made of 20.2 mole of polymerized of 15 moles of formic acid, 5 moles of M-phthalic acid and 4,4 '-diacetoxy biphenyl.
The fusing point of the aromatic polyester is 340 DEG C, in+30 DEG C of fusing point, shear velocity 1000sec-1When melt viscosity be 30Poise.
The aromatic polyester is 24 hours dry in 140 DEG C of vacuum drier, after moisture rate becomes 5ppm, squeezed using single screw rod
Machine melting extrusion out is measured using gear pump, and resin is supplied spinning packet.Slave outlet of extruder at this time is to spinning packet
Spinning temperature is 360 DEG C.Using the spinning head with the hole that 48 apertures are 0.09mm with spray volume 11.6cc/ minutes by resin
It sprays.Give finish to the resin of ejection, import the first godet, be then directed into the second godet, 48 monofilament simultaneously with
On reel, aromatic polyester fiber is obtained within 867m/ minutes.Winding tension (spinning winding tension) at this time is 20cN.
In about 120 minutes windings, there is no silk fracture, spinning operability is good.In addition, the total fiber number of obtained fiber is
144.3dtex, intensity 7.1cN/dtex, elongation 2.1%, elasticity modulus 480cN/dtex.Then, with 300m/ points
Clock is on from spinning reel warp to heat treatment reel.In the warp of 50000m, there is no single wire fractures and silk to be broken, winding
It can implement well, operability is also good.After the fiber is handled 10 hours in nitrogen with 310 DEG C, with 300m/ minutes from
It is heat-treated reel and carries out warp to paper tube.In the warp of 50000m, there is no single wire fractures and silk to be broken, and winding can be good
Implement well, operability is also good.In addition, having obtained total fiber number 144.3dtex, filament number about obtained fiber
3.0dtex, intensity 26.0cN/dtex, elongation 2.4%, elasticity modulus 1000cN/dtex fiber.On paper tube
The villus number of fiber is 0 in 1,000,000 m measurement after heat treatment, there is good quality.In addition, being led in guide rail operation test
The amount of deposit on rail is also few, and process passability is good.Above-mentioned spinning condition and result are shown in Table 1 below together.
[embodiment 2~16]
Using the aromatic polyester used in embodiment 1, in addition to changing total fiber number, filament number, spinning as was the case with table 1
Other than silk winding tension, spinning is carried out similarly to Example 1, obtains aromatic polyester fiber.Then, similarly to Example 1, will
Obtained aromatic polyester fiber is handled in nitrogen on from spinning reel warp to heat treatment reel, is rolled up from heat treatment
On cylinder warp to paper tube, the aromatic polyester fiber after being heat-treated.As shown in table 1, the warp of aromatic polyester fiber exists
All there is no single wire fractures and fracture of wire for heat treatment front and back, are good.The villus number of fiber after heat treatment is surveyed in 1,000,000 m
It is also 0 in fixed, there is good quality.The amount of deposit in guide rail operation test on guide rail is also few, and process passability is good
It is good.
[embodiment 17,18]
Using in+30 DEG C of fusing point, shear velocity 1000sec-1When melt viscosity be 20Poise and 40Poise fragrance
Adoption ester carries out spinning similarly to Example 1, obtains aromatic polyester fiber other than changing spinning temperature.Then, with
Embodiment 1 is same, by obtained aromatic polyester fiber on from spinning reel warp to heat treatment reel, in nitrogen
Reason, the aromatic polyester fiber from heat treatment reel warp to paper tube, after being heat-treated.As shown in table 1, aromatic polyester
The warp of fiber before heat treatment after all there is no single wire fractures and fracture of wire, be good.The villus of fiber after heat treatment
Number is also 0 in 1,000,000 m measurement, there is good quality.The amount of deposit in guide rail operation test on guide rail is also few,
Process passability is good.
[comparative example 1]
Other than being 4cN by spinning winding tension change, resin is sprayed similarly to Example 1, finish is given and is spun
Silk.However, just on reel 9, silk just falls off from godet 8 volume, and silk fracture immediately occurred.
[comparative example 2]
Fragrant adoption other than being 70cN by spinning winding tension change, after being heat-treated similarly to Example 1
Ester fiber.The warp of aromatic polyester fiber before heat treatment after single wire fracture and fracture of wire, the fiber after heat treatment all has occurred
Villus number 1,000,000 m measurement in be 98, poor quality.Deposit in guide rail operation test on guide rail generates in large quantities,
Process passability is poor.
[reference example 1]
Other than filament number is changed into 5.0dtex, spinning is equally carried out with comparative example 1.However, just volume is in reel
On 9, silk just falls off from godet 8, and silk fracture immediately occurred.
[reference example 2]
Other than filament number is changed into 5.0dtex, the aromatic polyester after heat treatment is similarly obtained with comparative example 2
Fiber.The warp of aromatic polyester fiber before heat treatment after all there is no single wire fractures and fracture of wire, be good.In addition,
The villus number of fiber after heat treatment is also 0 in 1,000,000 m measurement, there is good quality.The guide rail in guide rail operation test
On deposit amount it is also few, process passability is good.
[comparative example 3,4]
In addition to using+30 DEG C of fusing point, shear velocity 1000sec-1When melt viscosity be 5Poise and 70Poise fragrance
Other than adoption ester, spinning is carried out similarly to Example 1, but comparative example 3,4 cannot all be wound.
[table 1]
As described above, about the melting anisotropy aromatic polyester fiber after the heat treatment of embodiment 1~18, silk quality
Well, when being processed into fabric, the fracture of wire in warping process and tram weaving does not occur, process passability is excellent.It is obtained by comparative example 2
To fiber there are warping process and tram be woven into fracture of wire, process passability is poor.
Industrial availability
Although thin using the melting anisotropy aromatic polyester fiber of the invention that manufacturing method as described above obtains,
But there is high-intensitive, high elastic modulus feature, single wire fracture and fibrillation does not occur, 1,000,000 m medium staple approximate numbers are less than 3, substantially
Improve rear process passability to degree.
Therefore, general industry material, electric material (especially as tension element), soil be can be widely applied to
The fields such as Wood construction material, vest, sport-utility, automotive part, rubber reinforcement material, acoustical material, general dress material.
As effective purposes, rope, mesh, fishing net, printed circuit board base fabric, air bag, dirigible, dome can be enumerated
With equal base fabric, jockey dress, fishing line, various lines (sailing boat, paraglider, balloon, kite string), shutter rope, screen window support line,
The power transfer line etc. of various lines, electric product and robot can enumerate print as particularly effective purposes in automobile and aircraft
Printed circuit board base fabric, especially as fiber number refinement requirement it is strong, for the raising of weavability, the raising of fabric quality
, must inhibit in process generate villus product disadvantage base fabric, be most suitable for use.
Symbol description
1 spinneret
2 spinning packets
3 spinning heads
4 heaters
5 heat-preservation cylinders
6 feeding means
7 first godets
8 second godets
9 reels.
Claims (6)
1. a kind of melting anisotropy aromatic polyester fiber, it is characterised in that:
Show that the filament number that anisotropic aromatic polyester is formed is 4.0dtex composite filament below when it is by melting,
Villus number in 1,000,000 m of filament length is less than 3.
2. melting anisotropy aromatic polyester fiber as described in claim 1, it is characterised in that:
Total fiber number is for 10dtex or more, 500dtex hereinafter, number of monofilaments is in the range of 3~1000.
3. melting anisotropy aromatic polyester fiber as claimed in claim 1 or 2, it is characterised in that:
It is the fiber after heat treatment.
4. melting anisotropy aromatic polyester fiber as claimed in claim 1 or 2, it is characterised in that:
50000m warp is subjected to warp single wire fracture can not occur when on product paper tube.
5. melting anisotropy aromatic polyester fiber as claimed in claim 1 or 2, it is characterised in that:
Make the ceramic rod guide rail contact of fiber and diameter 4mm and in 300m/min, tension 120g/cm with 60 ° of contact angle2Condition
Under when running the silk of 10,000 m, the accumulating amount of the attachment on guide rail is less than 1mg.
6. a kind of melting anisotropy aromatic polyester composite filament, it is characterised in that:
It is obtained from spinning winding tension is set as 5cN or more, 60cN or less in melt spinning, and the melting is each to different
Property aromatic polyester composite filament filament number be 4.0dtex or less.
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| CN201910762745.4A CN110484992B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
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| PCT/JP2015/060292 WO2016047179A1 (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
| CN201910762745.4A CN110484992B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
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| KR (1) | KR101969558B1 (en) |
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|---|---|---|---|---|
| JPS6245726A (en) * | 1985-08-23 | 1987-02-27 | Sumitomo Chem Co Ltd | Production of aromatic polyester fiber |
| JP2006299474A (en) * | 2005-04-22 | 2006-11-02 | Kuraray Co Ltd | Ultrafine melt-anisotropic aromatic polyester fiber |
| JP2010084301A (en) * | 2008-10-02 | 2010-04-15 | Toray Ind Inc | Liquid-crystal polyester fiber |
| JP2012158851A (en) * | 2011-02-01 | 2012-08-23 | Kb Seiren Ltd | Method for manufacturing aromatic polyester fiber |
| JP2013133576A (en) * | 2011-12-27 | 2013-07-08 | Toray Ind Inc | Liquid crystal polyester multifilament |
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| JPH06166909A (en) * | 1992-09-30 | 1994-06-14 | Kuraray Co Ltd | Production of melt anisotropic aromatic polyester ultrafine fiber |
| JP3913527B2 (en) * | 2001-10-30 | 2007-05-09 | ポリプラスチックス株式会社 | Totally aromatic polyesteramide and polyesteramide resin composition |
| JP2005035714A (en) * | 2003-07-18 | 2005-02-10 | Toray Ind Inc | Yarn winder and yarn winding method |
| JP4983689B2 (en) * | 2008-03-28 | 2012-07-25 | 東レ株式会社 | Method for producing liquid crystal polyester fiber |
| US9011743B2 (en) * | 2009-03-11 | 2015-04-21 | Toray Industries, Inc. | Liquid crystal polyester fibers and method for producing the same |
| JP2010216052A (en) | 2009-03-19 | 2010-09-30 | Kuraray Co Ltd | Sea-island type conjugate fiber and ultrafine melt-anisotropic aromatic polyester fiber obtained from the sea-island type conjugate fiber |
| JP5327109B2 (en) * | 2009-03-23 | 2013-10-30 | 東レ株式会社 | Liquid crystalline polyester fiber and winding package |
| EP2695905B1 (en) * | 2011-04-01 | 2021-01-27 | Polyplastics Co., Ltd. | Fully aromatic polyester and polyester resin composition |
| JP6121867B2 (en) * | 2013-10-18 | 2017-04-26 | Ｋｂセーレン株式会社 | Method for producing aromatic polyester fiber |
| JP6121866B2 (en) * | 2013-10-18 | 2017-04-26 | Ｋｂセーレン株式会社 | Method for producing aromatic polyester fiber |
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- 2015-03-31 JP JP2016549971A patent/JP6608376B2/en active Active
- 2015-03-31 CN CN201910762745.4A patent/CN110484992B/en active Active
- 2015-03-31 CN CN201580011621.2A patent/CN106062260B/en active Active
- 2015-03-31 WO PCT/JP2015/060292 patent/WO2016047179A1/en active Application Filing
- 2015-03-31 KR KR1020167024121A patent/KR101969558B1/en active IP Right Grant
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6245726A (en) * | 1985-08-23 | 1987-02-27 | Sumitomo Chem Co Ltd | Production of aromatic polyester fiber |
| JP2006299474A (en) * | 2005-04-22 | 2006-11-02 | Kuraray Co Ltd | Ultrafine melt-anisotropic aromatic polyester fiber |
| JP2010084301A (en) * | 2008-10-02 | 2010-04-15 | Toray Ind Inc | Liquid-crystal polyester fiber |
| JP2012158851A (en) * | 2011-02-01 | 2012-08-23 | Kb Seiren Ltd | Method for manufacturing aromatic polyester fiber |
| JP2013133576A (en) * | 2011-12-27 | 2013-07-08 | Toray Ind Inc | Liquid crystal polyester multifilament |
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| Publication number | Publication date |
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| JPWO2016047179A1 (en) | 2017-07-06 |
| CN106062260B (en) | 2019-09-17 |
| KR20170034784A (en) | 2017-03-29 |
| CN110484992B (en) | 2023-05-30 |
| TWI650453B (en) | 2019-02-11 |
| WO2016047179A1 (en) | 2016-03-31 |
| JP6608376B2 (en) | 2019-11-20 |
| TW201612370A (en) | 2016-04-01 |
| CN106062260A (en) | 2016-10-26 |
| KR101969558B1 (en) | 2019-04-16 |
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