CN106062260A - Melt anisotropic aromatic polyester fiber and method for producing same - Google Patents
Melt anisotropic aromatic polyester fiber and method for producing same Download PDFInfo
- Publication number
- CN106062260A CN106062260A CN201580011621.2A CN201580011621A CN106062260A CN 106062260 A CN106062260 A CN 106062260A CN 201580011621 A CN201580011621 A CN 201580011621A CN 106062260 A CN106062260 A CN 106062260A
- Authority
- CN
- China
- Prior art keywords
- aromatic polyester
- fiber
- spinning
- melted
- polyester fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
Provided is a high-quality melt anisotropic aromatic polyester fiber which does not undergo fibrillation, single yarn breakage or the like during a rewinding process and a heat treatment process and therefore has excellent post-process passability in spite of the fact that the fiber has a small single yarn fineness degree. A melt anisotropic aromatic polyester fiber characterized by being a multi-filament which comprises an aromatic polyester that can exhibit anisotropic properties upon melting and which has a single yarn fineness degree of 4.0 dtex or less, and also characterized in that the number of fluffs is less than 3 per 1,000,000 m of the fiber. It is preferred that the aromatic polyester fiber has a total fineness degree of 10 to 500 dtex inclusive and the number of filaments falls within the range from 3 to 1000.
Description
Technical field
The fiber fines that the present invention relates to be formed by melted anisotropy aromatic polyester (filament number be 4.0dtex with
Under composite filament).
Background technology
Melted anisotropy aromatic polyester is the polymer formed by the strand of rigidity, in melt spinning, permissible
Make strand height-oriented along fiber axis direction.Additionally, it is known that due to melted anisotropy aromatic polyester with solid state also
Carry out polyreaction, by high temperature the fiber after spinning being carried out heat treatment, solid phase occurs, utilize melted spinning
The fiber that obtains of silk can become the highest intensity, elastic modelling quantity.Due to these characteristics, at present, melted anisotropy fragrance
Adoption ester fiber has been used in the yarn fabric of silk screen printing, coarse cloth, the line reinforcement material of various electric product, protecting hand
Bag, the reinforcement material of plastics, the tension element of optical fiber.It addition, in recent years, due to low-k and low-dielectric loss angle tangent
Such high frequency characteristics and excellent in dimensional stability, be expected to for use in printed circuit board base fabric.It addition, recently, along with
Mobile phone and PC, the miniaturization of panel computer, slimming, it is contemplated that to total fiber number, thinner the melting of filament number
The demand of anisotropy aromatic polyester fiber.
But, height-oriented melted anisotropy aromatic polyester fiber is low due to extension at break degree, drawing after spinning
Stretch and be nearly impossible.Therefore, in order to make filament number attenuate, target filament number must be become in the stage of spinning.Make
For the manufacture method of the thin melted anisotropy aromatic polyester fiber of filament number, such as propose in patent documentation 1 with
Under method: by multiple for the fabric of island-in-sea type with water-dispersible polyester as sea component, with melted anisotropy aromatic polyester as island component
Condensating fiber is rolled into cheese, in water, sea component is carried out dissolution process with its cheese form, thus obtains filament number and is
0.05～1.0dtex and heat treatment after the melted anisotropy aromatic polyester fiber that intensity is more than 20cN/dtex.
It addition, propose the manufacture method of melted anisotropy aromatic polyester superfine fibre in patent documentation 2, it is special
Levy and be: enter spraying the aromatic polyester that can form anisotropy melting behaviors from the nozzle of the pore of below diameter 0.1mm
In row spinning the melt spinning method that winds, use following condition (1)～(7).
(1) use is in shear rate 1000sec of the fusing point+20 DEG C of melted anisotropy aromatic polyester-1Time melted
The viscosity polymer less than 500Poise；(2) 10 will be set to by shear rate during nozzle3～109sec-1；(3) by nozzle
Ejection linear velocity be set to more than 5m/ minute less than 40m/ minute；(4) winding speed is set to more than 150m/ minute 8000m/
Below minute；(5) ratio that winding speed sprays linear velocity relatively is set to more than 20；(6) spinneret temperature is set to fusing point+15
More than DEG C；(7) temperature of fiber during distance nozzle face 30cm less than Tm-150 DEG C will be set to after ejection.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-216052 publication
Patent documentation 2: Japanese Unexamined Patent Publication 6-166909 publication
Summary of the invention
Invent problem to be solved
But, in the method for patent documentation 1, after islands-in-sea bicomponent fibre warp is become cheese, in water at dissolving
Reason is required, therefore after easy zbility become difficulty.It addition, can cause between monofilament when carrying out heat treatment is deadlocked, because of
This makes a quality variation due to the single wire fracture in afterwards unwinding and fibrillation.
In contrast, in the method for patent documentation 2, it is possible to use common spinning head is steady to the fiber of thin filament number
Surely carry out spinning, there is the cheap such advantage of cost, but during the fiber in carrying out warp etc. unwinding, easily cause because of every
Fibrillation, single wire fracture and the fracture of wire that the intensity of 1 monofilament declines and causes, the poor quality of obtained fiber.
It is an object of the invention to: the melted of a kind of thin and that fibrillation and single wire fracture etc. do not occur high-quality is provided
Anisotropy aromatic polyester fiber.
For the method solving problem
The present inventor studies intensively, found that the present invention.That is, the purpose of the present invention by provide one melted each to
The opposite sex aromatic polyester fiber and reach, this melted anisotropy aromatic polyester fiber is characterised by: it is by time melted
Show the composite filament that filament number is below 4.0dtex that anisotropic aromatic polyester is formed, the floss in filament length 1,000,000 m
Approximate number is less than 3.The preferred total fiber number of this aromatic polyester fiber is more than 10dtex, below 500dtex, and monofilament number is 3～1000
In the range of.It addition, the present invention also provides for a kind of method manufacturing above-mentioned melted anisotropy aromatic polyester fiber, the method
To showing time melted that anisotropic aromatic polyester carries out melt spinning, obtaining filament number is the compound of below 4.0dtex
Silk, in the method, uses in fusing point+30 DEG C, shear rate 1000sec-1Time melt viscosity be more than 10Poise,
The aromatic polyester of below 50Poise, is set to more than 5cN, below 60cN by spinning winding tension force.
Invention effect
Although the melted anisotropy aromatic polyester fiber filament number of the present invention is below 4.0dtex, but it is one
Plant the rear operation that single wire fracture and fibrillation the do not occur fiber by the high-quality of property excellence.
Accompanying drawing explanation
Fig. 1 is the explanatory diagram of the outline of the example representing the melt spinning device used in the present invention.
Detailed description of the invention
Hereinafter, the present invention is described in detail.
Aromatic polyester in the present invention shows anisotropic aromatic polyester when being melted.So-called this melted time aobvious
Show that anisotropic aromatic polyester refers to the aromatic polyester with aftermentioned character, i.e. inclined being present in 90 ° of orthogonal 2 piece
When placing polyester sample powder on the heating sample platform between tabula rasa and heat up, within the temperature range of can flowing, can
With the character through light.As such aromatic polyester, it is by Japanese Patent Publication 56-18016 publication and Japanese Patent Publication
Aromatic dicarboxylic acid, aromatic diol and/or aromatic hydroxy-carboxylic shown in 55-20008 publication etc. and they
The aromatic polyester that derivant is formed, according to circumstances, also include above-claimed cpd and alicyclic dicarboxylic acid, cycloaliphatic diols,
Aliphatic dihydroxy alcohol and the copolymer of their derivant.Wherein, as aromatic dicarboxylic acid, terephthaldehyde can be enumerated
Acid, M-phthalic acid, 4,4 '-dicarboxylate biphenyl, 2,6-dicarboxyl naphthalene, double (4-carboxyphenoxy) ethane of 1,2-etc. and general
The hydrogen of these aromatic rings utilizes the compound after the replacement of alkyl, aryl, alkoxyl, halogen.As aromatic diol, permissible
Enumerate hydroquinone, resorcinol, 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxy benaophenonel, 4,4 '-dihydroxy hexichol
Double (4-hydroxy phenyl) propane of methane, 4,4 '-dihydroxy diphenylethane, 2,2-, 4,4 '-dihydroxy diphenyl ether, 4,4 '-
Dihydroxydiphenylsulisomer, 4,4 '-dihydroxy diphenyl sulfide, 2,6-dihydroxy naphthlene, 1,5-dihydroxy naphthlene etc. and by these fragrance
The hydrogen of ring utilizes the compound after the replacement of alkyl, aryl, alkoxyl, halogen.As aromatic hydroxy-carboxylic, can enumerate 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 utilize alkyl, aryl, alkoxyl, halogen replace after compound.As alicyclic dicarboxylic acid, anti-form-1 can be enumerated,
4-dicarboxyl hexamethylene, cis-1,4-dicarboxyl hexamethylene etc. and the hydrogen of these aromatic rings is utilized alkyl, aryl, alkane
Compound after the replacement of epoxide, halogen.As alicyclic and aliphatic dihydroxy alcohol, anti-form-1,4-dihydroxy basic ring can be enumerated
Hexane, cis-1,4-dihydroxy hexamethylene, ethylene glycol, 14-butanediol, xyxylene glycol etc..
In these combinations, as preferred aromatic polyester in the present invention, comprise hydroxyl for example, it is possible to enumerate (1)
Yl benzoic acid residue and/or 2 hydroxy naphthalene-6-carboxylic acid residues 40～70 moles of %, above-mentioned aromatic dicarboxylic acid residue 15～
30 moles of % and aromatic diol residue 15～the copolyesters of 30 moles of %；(2) by p-phthalic acid and/or M-phthalic acid
The copolyesters formed with Adurol, phenyl hydroquinone and/or hydroquinone；(3) P-hydroxybenzoic acid is comprised residual
Base 20～80 moles of % and 2 hydroxy naphthalene-6-carboxylic acid residues 20～the copolyesters etc. of 80 moles of %.
When using these raw materials to obtain aromatic polyester used in the present invention, can be used as it is or utilize fat
The esterification of fat race or aromatic monocarboxylate or their derivant, aliphatic alcohol or phenols or their derivant etc. carries out polycondensation
Reaction.As polycondensation reaction, can use known bulk polymerization, polymerisation in solution, suspended polymerization etc., the polymer obtained is permissible
Former state as spinning sample, or can also using powder shaped in inactive gas or decompression under carry out heat treatment after as spinning
Silk sample.Or, utilize extruder to use after carrying out first pelletize.
The most do not reduce in the range of the physical property of melted anisotropy aromatic polyester fiber, it is also possible in composition
Comprise other polymer or additive (pigment, carbon, heat stabilizer, UV absorbent, lubricant, fluorescent whitening agent
Deng).
In the aromatic polyester of the present invention, there is the molecular weight ranges being suitable to spinning." flow starting temperature " is used to make
For the physics value corresponding with the molecular weight being suitable to this melt spinning condition.About " flow starting temperature ", Shimadzu is used to make
Made flow tester CFT-500, utilizes the nozzle of diameter 1mm, length 10mm, at pressure 100kg/cm2State under,
With 4 DEG C/min, aromatic polyester sample is heated up, make sample pass through Flow in Nozzle and give 4, the table of 800 pascal seconds
See viscosity, temperature now is defined as " flow starting temperature ".
" flow starting temperature " about the melted anisotropy aromatic polyester of the present invention is suitably for 290～330 DEG C.
The filament number of the melted anisotropy aromatic polyester fiber of the present invention is below 4.0dtex, is preferably
Below 2.5dtex, more preferably below 1.0dtex.Total fiber number range preferably from more than 10dtex, below 500dtex, more
Add preferably more than 15dtex, below 450dtex, more preferably more than 20dtex, below 400dtex.The model of monofilament number
Enclose preferably 3～1000, more preferably 10～800, more preferably 20～600.
About the melted anisotropy aromatic polyester being suitable to melt spinning of the present invention, in fusing point+30 DEG C, shear rate
1000sec-1Time melt viscosity be more than 10Poise, below 50Poise.As long as it is single within the range, to be adapted to stable manufacture
Silk size is the aromatic polyester fiber of below 4.0dtex.During it is to say, melt viscosity is less than 10Poise, squeeze from spinning head
The polymer gone out easily becomes drops, there is the tendency that the stability of spinning is not enough.When melt viscosity is more than 50Poise, by
Reduce in draging a property, have and attenuate along with fiber number and the danger of single wire fracture occurs, there is the tendency that the stability of spinning is not enough.
It addition, about melt viscosity, use capillary rheometer (CAPILOGRAPH) (Toyo Seiki makes made pattern 1B), utilize
Diameter 0.5mm, the nozzle of length 5mm, heat up to aromatic polyester sample with fusing point+30 DEG C, when sample is by nozzle,
Apply 1000sec-1Shear rate, viscosity now is defined as melt viscosity.
By using the aromatic polyester fiber of the melt spinning device manufacture present invention the most as shown in Figure 1.At Fig. 1
In, 1 is spinneret, and 2 is spinning bag, and 3 is spinning head, and 4 is heater, and 5 is heat-preservation cylinder.
In melt spinning, known method can be used about melt extruding of aromatic polyester.In order to be suitable to melt
Spinning, is generally granulated aromatic polyester, uses the extruder of extruder type.The resin of extrusion, by pipe arrangement, is sent to spin
Silk 1, utilizes the known metering devices (not shown) such as gear pump to measure, and by after filter in spinning bag 2, enters
Spinning head 3.Below more than the fusing point of aromatic polyester, heat decomposition temperature will be set to the temperature of spinning head 3 from polymer pipe arrangement
It is suitable.
By arranging heater 4 and heat-preservation cylinder 5 directly below at spinning head 3, the diameter that can make the fiber of ejection is steady
Fixedization, and the change of atmosphere temperature below the surface temperature of spinning head that caused by outside gas and spinning head can be suppressed
Change, make the refinement utilizing air-flow become uniform, there is no silk fracture and fine hair generation etc., exist and easily become inclining of stable spinning
To.
It addition, the shear rate in spinneret hole is set to 104～105sec-1It is suitable.Following formula is utilized to obtain this
Shear rate γ of bright middle indication.
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))
Time within the above range, the orientation of fiber can become abundant, exists and is readily obtained the thin fiber of fiber number and easy
Tendency to target properties.
It addition, during for aromatic polyester fiber, be tired owing to the rear operation after spinning winding carrying out stretching
Difficult, therefore to obtain the composite filament that filament number is below 4.0dtex, it is suitable for utilizing pore ejection resin as much as possible
's.Therefore, the aperture (diameter) of spinning head is preferably below 0.2mm, more preferably below 0.18mm.
As it has been described above, after aromatic polyester fiber after utilizing feeding means 6 to give spinning by the oil preparation of regulation, utilize
First godet 7 and the second godet 8 are pulled, and are wound on reel 9 (spinning reel).Winding speed is preferably 400m/ minute
Above, less than 2000m/ minute, more preferably more than 600m/ minute, less than 1800m/ minute.The second godet 8 with
The spinning winding tension force measured between spinning reel 9 is preferably more than 5cN, below 60cN, more preferably more than 10cN, 50cN
Hereinafter, more preferably more than 20cN, below 40cN.When tension force is less than 5cN, a twisting cohesion can be made at seal wire because fiber is lax
On roller 8, cause the shape defect of reel 9.In warp operation later, there occurs that the reel of shape defect is because falling silk etc. easily
There is fracture of wire and single wire fracture, make productivity ratio and quality decline.Generally, as long as the fiber that filament number is more than 4.0dtex, i.e.
Make spinning winding tension force 70～about 100cN, the shape of spinning reel also will not deform and can with stable roll around, if but single
Silk size is at below 4.0dtex, when spinning winding tension force is more than 60cN, will cause the silk fracture in spinning and later anti-
Single wire fracture in volume operation, fibrillation, make productivity ratio and quality decline.It addition, in the present invention, spinning winding tension force represents
The value that the tension force applied during winding on reel 9 is measured.
Manufacture the present invention aromatic polyester fiber time, spinning winding tension force is set to more than 5cN, 60cN the following is weight
Want.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
Crossing 4.0dtex, the intensity of generally every monofilament is at more than 20cN.When filament number becomes below 4.0dtex, every monofilament strong
Degree will step-down, even the damage of a little the most easily causes fibrillation, single wire fracture and fracture of wire.It addition, aromatic polyester
Fiber is compared with general polyester fiber, and elongation is extremely low, therefore can not absorb the tension force being applied on fiber, also become fibril
Change and the reason of fracture of wire.During it addition, filament number becomes below 4.0dtex, the volume density of spinning reel will uprise.This
Time, owing to overlapping monofilament is absorbed in the most each other, when carrying out unwinding to the fiber of spinning reel, monofilament is done each other, thus
Cause fibrillation and single wire fracture etc..Therefore, in the present invention, during spinning, winding tension is set to more than 5cN, below 60cN,
The load being applied on silk when alleviating spinning winding as much as possible, does one's utmost to reduce the volume density of spinning reel, alleviates monofilament
It is absorbed in, prevents fibrillation, single wire fracture and fracture of wire, thus make melted anisotropy aromatic polyester fiber become high-quality.
For the melted anisotropy aromatic polyester fiber utilizing above-mentioned manufacture method to obtain, even filament number
For the fine fibre of below 4.0dtex, in warp described later and heat treatment, single wire fracture and fibrillation also will not occur, afterwards
Operation by property the most excellent, be the fiber of a kind of high-quality.
The intensity of the fiber above-mentioned melted anisotropy aromatic polyester being carried out melt spinning and obtain is preferably
More than 3.0cN/dtex, more preferably more than 5.0cN/dtex.It addition, elongation is preferably more than 0.5%, it is more preferably
More than 1.0%.It addition, elastic modelling quantity is preferably more than 300cN/dtex, more preferably more than 400cN/dtex.
The melted anisotropy aromatic polyester fiber utilizing spinning to obtain can be used as it is, it is also possible to passes through heat treatment
High intensity, high resiliency further.In this case, before heat treatment, preferably by the fiber of spinning reel temporarily to it
Its heat treatment reel warp becomes bag.Now, as it has been described above, by the spinning winding tension force in spinning process is set to 5cN
Above, below 60cN, the easy zbility of the fiber in warp can be made to become good, do not occurred single wire fracture and silk fracture
The silk of high-quality.When heat treated is with reel warp, in order to carry out solid phase equably, the volume density of bag is preferably
More than 0.01g/cc, below 1.0g/cc, more preferably below 0.8g/cc.Wherein, so-called volume density, from by wrapping
The possessive volume Vf (cc) of the fiber that the outside dimension of size and the heat treatment reel that becomes core is obtained and quality Wf of fiber
G (), utilizes the value that Wf/Vf calculates.Survey it addition, possessive volume Vf is the overall dimensions to bag, and assume the volume of warp
Cylinder is value that is rotationally symmetrical, that obtained by calculating, before and after Wf is the value calculated by fiber number and spooling length or utilization winding
The value of actual measurement of poor quality.In order to make volume density step-down, preferably warp speed is set to less than 500m/ minute, more preferably
For less than 400m/ minute.
It is suitable for carrying out heat treatment with the temperature below the fusing point of above-mentioned melted anisotropy aromatic polyester fiber.By
This, can carry out the solid phase of aromatic polyester fiber, improves intensity, elastic modelling quantity.It addition, when heat treatment, there is fibre
Between dimension, the tendency of easily fusion, therefore to prevent interfibrous fusion, periodically rises to the temperature of below fusing point from room temperature
Degree is suitable.
In order to stably carry out the solid phase in heat treatment, under inactive gas atmosphere, preferably carry out heat treatment.But
It is that, from the standpoint of cost, in the case of using dry air, dehumidifying is to dew point less than-40 DEG C the most in advance.That is, as
Really there is moisture during solid phase, induce hydrolysis sometimes, it is impossible to improve intensity fully.
Bag can also former state be provided by the fiber after heat treatment as goods, but in order to improve goods 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 right from alleviating
From the standpoint of the damage of fiber, preferably less than 500m/ minute, more preferably less than 400m/ minute.
As it has been described above, by heat treatment can further production efficiency highly stably obtain high intensity, high elastic modulus,
The melted anisotropy aromatic polyester fiber that quality is the highest.Heat treatment proceeded as above and the intensity of fiber that obtains is preferred
For more than 10.0cN/dtex, more preferably more than 12.0cN/dtex, more preferably more than 20.0cN/dtex.It addition,
Elongation is preferably more than 1.0%, and more preferably more than 2.0%.It addition, elastic modelling quantity is preferably more than 400cN/dtex,
It is more preferably more than 500cN/dtex.
The melted anisotropy aromatic polyester fiber of the present invention is that the fine hair number in filament length 1,000,000 m is less than 3, in weaving
The fiber of high-quality no problem in operation after Deng.More preferably fine hair number is less than 2, is further preferably no larger than 1.Can utilize
Above-mentioned described manufacture method obtains such fiber.
Embodiment
Hereinafter, enumerate embodiment the present invention is specifically explained.Embodiment and comparative example use the melt spinning of Fig. 1
Device, carries out the spinning of aromatic polyester fiber.It addition, the present invention is not limited to embodiments discussed below.In embodiment
Each evaluation carry out as follows.
1) tension test (intensity, elongation, elastic modelling quantity)
According to test during the standard of JISL 1013 (2010), use the cupping machine AGS-of Shimadzu Seisakusho Ltd.
500NX, obtains rupture strength elongation and elastic modelling quantity (initial stage tension for 200mm/ minute with specimen length 200mm, draw speed
Intensity), represent with the meansigma methods of 10 points.
2) spinning winding tension force
Use electronic type tonometer CM-100R of Jin Jinggong machine Co., Ltd., in spinning winding, second to Fig. 1
Running tension between godet 8 and reel 9 carries out 3 times and measures, and represents with its meansigma methods.
3) spinning operability evaluation
Hereinafter spinning operability when carrying out spinning in more than 2 hours is evaluated.
Zero does not occur silk to rupture, and can stably carry out spinning.
△ there occurs the silk fracture within 5 times in the spinning of 2 hours.
× occur repeatedly silk to rupture, it is impossible to winding.
4) spinning precursor warp is evaluated
Hereinafter operability during by the fiber warp after 50000m spinning on ferrum reel is evaluated.
Zero there is not single wire fracture and silk fracture, can stably carry out warp.
△ there occurs single wire fracture and silk fracture.
× occurring repeatedly silk to rupture, it is impossible to warp is to last.
5) heat treatment silk warp is evaluated
Hereinafter operability during by the fiber warp after 50000m heat treatment on goods paper tube is evaluated.
Zero there is not single wire fracture and silk fracture, can stably carry out warp.
△ there occurs single wire fracture.
× occurring repeatedly silk to rupture, it is impossible to warp is to last.
6) fine hair number is evaluated
Use springtime electrically (Co., Ltd.) system, fine hair to find device F9-AN type, the fiber after heat treatment is measured 1,000,000 m
Filament length, as described below measurement result is evaluated.
Zero fine hair number is less than 1
△ fine hair number more than 1, less than 3
× fine hair number more than 3
7) guide rail operation test
The ceramic rod guide rail contact of fiber and diameter 4mm is made with contact angle 60 °, and at 300m/min, tension force 120g/cm2
Under conditions of make the heat treatment silk of 10,000 m run, operation is entered by the accumulating amount of the attachment from guide rail as described below by property
Row is evaluated.
Zero accumulating amount is less than 1mg
△ accumulating amount is more than 1mg, less than 3mg
× accumulating amount is more than 3mg
[embodiment 1]
As the melted anisotropic aromatic polyester of display, use by acetoxy-benzoic acid 40 moles, to benzene two
15 moles of formic acid, M-phthalic acid 5 moles and the aromatic polyester of 4,4 '-diacetoxy biphenyl 20.2 mole of polymerized.
The fusing point of this aromatic polyester is 340 DEG C, in fusing point+30 DEG C, shear rate 1000sec-1Time melt viscosity be 30Poise.
This aromatic polyester is dried 24 hours in the vacuum drier of 140 DEG C, after moisture rate becomes 5ppm, utilizes single screw rod to squeeze
Go out machine to melt extrude, utilize gear pump to measure, resin is supplied spinning bag.Now from outlet of extruder to spinning bag
Spinning temperature is 360 DEG C.Utilize and there is the spinning head in the hole that 48 apertures are 0.09mm with spray volume 11.6cc/ minute by resin
Ejection.Resin to ejection gives oil preparation, imports the first godet, is then directed into the second godet, 48 monofilament simultaneously with
Within 867m/ minute, it is wound on reel, obtains aromatic polyester fiber.Winding tension (spinning winding tension force) now is 20cN.
In the winding of about 120 minutes, not occurring silk to rupture, spinning operability is good.It addition, the total fiber number of the fiber obtained is
144.3dtex, intensity is 7.1cN/dtex, and elongation is 2.1%, and elastic modelling quantity is 480cN/dtex.Then, divide with 300m/
Clock is from spinning reel warp to heat treatment reel.In the warp of 50000m, there is not single wire fracture and silk fracture, winding
Can implement well, operability is the best.After this fiber being processed 10 hours in nitrogen with 310 DEG C, with 300m/ minute from
Heat treatment reel carries out warp to paper tube.In the warp of 50000m, single wire fracture and silk fracture not occurring, winding can be good
Implementing well, operability is the best.It addition, about the fiber obtained, obtained total fiber number 144.3dtex, filament number
3.0dtex, intensity 26.0cN/dtex, elongation 2.4%, the fiber of elastic modelling quantity 1000cN/dtex.It is wound on paper tube
After heat treatment, the fine hair number of fiber is 0 in 1,000,000 m measure, and has good quality.It addition, lead in guide rail operation test
The amount of the deposit on rail is also few, and operation is good by property.Above-mentioned spinning condition is shown in Table 1 below together with result.
[embodiment 2～16]
Use the aromatic polyester used in embodiment 1, except changing total fiber number, filament number as was the case with table 1, spinning
Beyond silk winding tension, carry out spinning similarly to Example 1, obtain aromatic polyester fiber.Then, similarly to Example 1, will
The aromatic polyester fiber obtained, from spinning reel warp to heat treatment reel, processes in nitrogen, rolls up from heat treatment
Cylinder warp, on paper tube, obtains the aromatic polyester fiber after heat treatment.As shown in table 1, the warp of aromatic polyester fiber exists
The most there is not single wire fracture and fracture of wire before and after heat treatment, be good.The fine hair number of the fiber after heat treatment is surveyed at 1,000,000 m
Also it is 0 in Ding, has good quality.The amount of the deposit on guide rail operation test middle guide is also few, and operation is good by property
Good.
[embodiment 17,18]
Use in fusing point+30 DEG C, shear rate 1000sec-1Time the fragrance that melt viscosity is 20Poise and 40Poise
Adoption ester, in addition to change spinning temperature, carries out spinning similarly to Example 1, obtains aromatic polyester fiber.Then, with
Embodiment 1 is same, by the aromatic polyester fiber that obtains from spinning reel warp to heat treatment reel, locates in nitrogen
Reason, from heat treatment reel warp to paper tube, obtains the aromatic polyester fiber after heat treatment.As shown in table 1, aromatic polyester
The warp of fiber before heat treatment after the most there is not single wire fracture and fracture of wire, be good.The fine hair of the fiber after heat treatment
Number is also 0 in 1,000,000 m measure, and has good quality.The amount of the deposit on guide rail operation test middle guide is also few,
It is good that operation passes through property.
[comparative example 1]
In addition to spinning winding tension change is 4cN, spray resin similarly to Example 1, give oil preparation and spin
Silk.But, just volume is on reel 9, and silk just comes off from godet 8, there occurs that silk ruptures at once.
[comparative example 2]
In addition to spinning winding tension change is 70cN, obtain the fragrant adoption after heat treatment similarly to Example 1
Ester fiber.The warp of aromatic polyester fiber before heat treatment after all there occurs single wire fracture and fracture of wire, the fiber after heat treatment
Fine hair number 1,000,000 m measure in be 98, poor quality.Deposit on guide rail operation test middle guide produces in large quantities,
It is poor that operation passes through property.
[reference example 1]
In addition to filament number is changed into 5.0dtex, carry out spinning as comparative example 1.But, just volume is at reel
On 9, silk just comes off from godet 8, there occurs that silk ruptures at once.
[reference example 2]
In addition to filament number is changed into 5.0dtex, it is similarly obtained the aromatic polyester after heat treatment with comparative example 2
Fiber.The warp of aromatic polyester fiber before heat treatment after the most there is not single wire fracture and fracture of wire, be good.It addition,
The fine hair number of the fiber after heat treatment is also 0 in 1,000,000 m measure, and has good quality.At guide rail operation test middle guide
On the amount of deposit also few, operation is good by property.
[comparative example 3,4]
Except using fusing point+30 DEG C, shear rate 1000sec-1Time the fragrance that melt viscosity is 5Poise and 70Poise
Beyond adoption ester, carry out spinning similarly to Example 1, but comparative example 3,4 all can not wind.
[table 1]
As it has been described above, about the melted 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 not occurring warping process and tram to inweave, operation is excellent by property.Obtained by comparative example 2
To fiber there is warping process and tram inweave in fracture of wire, operation is poor by property.
Industrial applicability
Although the melted anisotropy aromatic polyester fiber utilizing the present invention that manufacture method as described above obtains is thin,
But having the feature of high intensity, high elastic modulus, single wire fracture and fibrillation do not occur, 1,000,000 m medium staple approximate numbers are less than 3, significantly
Improve the rear operation property passed through degree.
Therefore, it can be widely used in general industry material, electric material (especially as tension element), soil
The fields such as Wood construction material, protective clothing, sport-utility, automotive part, rubber reinforcement material, acoustical material, general dress material.
As effective purposes, rope, net, fishing net, use in printed circuit board base fabric, air bag, dirigible, dome can be enumerated
With wait base fabric, jockey dress, fishing line, various line (sailing boat, paraglider, balloon, kite string), shutter rope, screen window support line,
In automobile and aircraft, the power transfer line etc. of various lines, electric product and robot, as particularly effective purposes, can enumerate print
Printed circuit board base fabric, raising for weavability strong especially as the requirement of fiber number refinement, the raising of fabric quality
, must suppress to produce the base fabric of the goods shortcoming of fine hair in operation, be best suitable for use.
Symbol description
1 spinneret
2 spinning bags
3 spinning heads
4 heaters
5 heat-preservation cylinders
6 feeding means
7 first godets
8 second godets
9 reels
Claims (3)
1. a melted anisotropy aromatic polyester fiber, it is characterised in that:
It is by the composite filament that filament number is below 4.0dtex showing time melted that anisotropic aromatic polyester is formed,
Fine hair number in filament length 1,000,000 m is less than 3.
2. melted anisotropy aromatic polyester fiber as claimed in claim 1, it is characterised in that:
Total fiber number is more than 10dtex, below 500dtex, and monofilament number is in the range of 3～1000.
3. a manufacture method for aromatic polyester fiber, it is fine for the aromatic polyester described in manufacturing claims 1 or 2
Dimension, this manufacture method is characterised by:
To showing time melted that anisotropic aromatic polyester carries out melt spinning, obtaining filament number is below 4.0dtex's
Composite filament,
In this manufacture method, use in fusing point+30 DEG C, shear rate 1000sec-1Time melt viscosity be more than 10Poise,
The aromatic polyester of below 50Poise, spinning winding tension force is more than 5cN, below 60cN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910762745.4A CN110484992B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014197585 | 2014-09-26 | ||
| JP2014-197585 | 2014-09-26 | ||
| PCT/JP2015/060292 WO2016047179A1 (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910762745.4A Division CN110484992B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106062260A true CN106062260A (en) | 2016-10-26 |
| CN106062260B CN106062260B (en) | 2019-09-17 |
Family
ID=55580721
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580011621.2A Active CN106062260B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropy aromatic polyester fiber and its manufacturing method |
| CN201910762745.4A Active CN110484992B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910762745.4A Active CN110484992B (en) | 2014-09-26 | 2015-03-31 | Melt anisotropic aromatic polyester fiber and method for producing same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6608376B2 (en) |
| KR (1) | KR101969558B1 (en) |
| CN (2) | CN106062260B (en) |
| TW (1) | TWI650453B (en) |
| WO (1) | WO2016047179A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108505137A (en) * | 2018-03-27 | 2018-09-07 | 东华大学 | A kind of Thermotropic Liquid Crystalline Copolyesters fiber and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06166909A (en) * | 1992-09-30 | 1994-06-14 | Kuraray Co Ltd | Production of melt anisotropic aromatic polyester ultrafine fiber |
| JP2009235634A (en) * | 2008-03-28 | 2009-10-15 | Toray Ind Inc | Method for producing liquid crystal polyester fiber |
| JP2010084301A (en) * | 2008-10-02 | 2010-04-15 | Toray Ind Inc | Liquid-crystal polyester fiber |
| CN102348841A (en) * | 2009-03-11 | 2012-02-08 | 东丽株式会社 | Liquid crystal polyester fibers and method for producing the same |
| 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 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0814043B2 (en) * | 1985-08-23 | 1996-02-14 | 住友化学工業株式会社 | Heat treatment method for aromatic polyester 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 |
| JP2006299474A (en) * | 2005-04-22 | 2006-11-02 | Kuraray Co Ltd | Ultrafine melt-anisotropic aromatic polyester fiber |
| 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 |
| KR101413813B1 (en) * | 2011-04-01 | 2014-06-30 | 폴리플라스틱스 가부시키가이샤 | Fully aromatic polyester and polyester resin composition |
| JP6121866B2 (en) * | 2013-10-18 | 2017-04-26 | Ｋｂセーレン株式会社 | Method for producing aromatic polyester fiber |
| JP6121867B2 (en) * | 2013-10-18 | 2017-04-26 | Ｋｂセーレン株式会社 | Method for producing aromatic polyester fiber |
-
2015
- 2015-03-31 KR KR1020167024121A patent/KR101969558B1/en active IP Right Grant
- 2015-03-31 JP JP2016549971A patent/JP6608376B2/en active Active
- 2015-03-31 WO PCT/JP2015/060292 patent/WO2016047179A1/en active Application Filing
- 2015-03-31 CN CN201580011621.2A patent/CN106062260B/en active Active
- 2015-03-31 CN CN201910762745.4A patent/CN110484992B/en active Active
- 2015-04-01 TW TW104110608A patent/TWI650453B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06166909A (en) * | 1992-09-30 | 1994-06-14 | Kuraray Co Ltd | Production of melt anisotropic aromatic polyester ultrafine fiber |
| JP2009235634A (en) * | 2008-03-28 | 2009-10-15 | Toray Ind Inc | Method for producing liquid crystal polyester fiber |
| JP2010084301A (en) * | 2008-10-02 | 2010-04-15 | Toray Ind Inc | Liquid-crystal polyester fiber |
| CN102348841A (en) * | 2009-03-11 | 2012-02-08 | 东丽株式会社 | Liquid crystal polyester fibers and method for producing the same |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108505137A (en) * | 2018-03-27 | 2018-09-07 | 东华大学 | A kind of Thermotropic Liquid Crystalline Copolyesters fiber and preparation method thereof |
| CN108505137B (en) * | 2018-03-27 | 2020-08-11 | 东华大学 | Thermotropic liquid crystal polyarylester fiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170034784A (en) | 2017-03-29 |
| WO2016047179A1 (en) | 2016-03-31 |
| CN106062260B (en) | 2019-09-17 |
| JP6608376B2 (en) | 2019-11-20 |
| CN110484992A (en) | 2019-11-22 |
| KR101969558B1 (en) | 2019-04-16 |
| CN110484992B (en) | 2023-05-30 |
| TW201612370A (en) | 2016-04-01 |
| JPWO2016047179A1 (en) | 2017-07-06 |
| TWI650453B (en) | 2019-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI602963B (en) | Liquid crystal polyester fiber and method for preparing the same | |
| JP5791284B2 (en) | Method for producing aromatic polyester fiber | |
| CN106414820A (en) | Liquid crystal polyester fibers, and production method therefor | |
| CN110268109A (en) | Thermal bonding sheath-core type conjugate fiber and warp-knitted fabric | |
| JP5098693B2 (en) | Liquid crystal polyester fiber | |
| JP6855683B2 (en) | Liquid crystal polyester multifilament | |
| TW201035398A (en) | Polyester monofilament and method for manufacturing polyester monofilament | |
| US20150004409A1 (en) | Liquid-crystalline polyester multifilament | |
| JP5428271B2 (en) | Method for producing liquid crystal polyester fiber | |
| JP2010242246A (en) | Method for producing liquid crystal polyester fiber | |
| CN106062260A (en) | Melt anisotropic aromatic polyester fiber and method for producing same | |
| JP5327116B2 (en) | Liquid crystal polyester fiber and method for producing the same | |
| JP6121867B2 (en) | Method for producing aromatic polyester fiber | |
| CN113166978B (en) | Core-sheath composite polyester monofilament for high-definition high-mesh filter | |
| TW587108B (en) | A process for the spinning and spooling of polyester filaments, through the use of spinning additives polyester filaments which can be obtained by means of the spinning process, the stretch texturing of the polyester filaments, as well as bulky polyester | |
| JP6121866B2 (en) | Method for producing aromatic polyester fiber | |
| JP6953776B2 (en) | Liquid crystal polyester multifilament | |
| KR20240066260A (en) | Liquid crystal polyester fiber and method for producing the same | |
| JP5239454B2 (en) | Liquid crystal polyester fiber and method for producing the same | |
| JPS591710A (en) | Poly(p-phenylene terephthalamide) fiber of novel structure and its preparation | |
| JP2015030920A (en) | Liquid crystalline polyester fiber and method for producing the same | |
| TW491915B (en) | Elastanes of coarse linear density and their production by wet spinning | |
| JP2009052161A (en) | Conjugated fiber | |
| JPH05230711A (en) | Production of p-orientated type aramid fiber | |
| JPS63249778A (en) | Antifungal aramide fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |