CN101946031B - Fiber and process for producing the same - Google Patents
Fiber and process for producing the same Download PDFInfo
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- CN101946031B CN101946031B CN2009801049385A CN200980104938A CN101946031B CN 101946031 B CN101946031 B CN 101946031B CN 2009801049385 A CN2009801049385 A CN 2009801049385A CN 200980104938 A CN200980104938 A CN 200980104938A CN 101946031 B CN101946031 B CN 101946031B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
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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
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- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
A fiber is provided which is made only of a polymer having crystallinity and has voids in inner parts thereof. Also provided is a process for producing the fiber. The process for fiber production includes: a melt spinning step in which a resin composition comprising a polymer having crystallinity as the only polymer ingredient is melt-spun; and a stretching step in which stretching is conducted at a speed of 10-2,000 m/min and at a stretching temperature (T, DEG C) satisfying the relationship represented by (Tg-30)<=T<=(Tg+50), wherein T ( DEG C) is the stretching temperature and Tg ( DEG C) is the glass transition temperature of the polymer having crystallinity.
Description
Technical field
The present invention relates to a kind of light weight sense excellence, have reflexive fiber and manufacturing approach thereof.
Background technology
In recent years, for the functional or taste that makes fiber improves, carry out various effort always.For example, change, make water imbibition to improve or make polymer modification improve light weight or make the raising of fibrillation property through the cross sectional shape that makes fiber, or make dark color property raising (with reference to patent documentation 1).
On the other hand; For the taste that makes fiber improves; Motion has various composite fibres etc., thereby said composite fibre has two kinds of different polymer of alternately laminated refractive index and they are covered the function (with reference to patent documentation 2) that manifests structural colour developing with protective layer.
But, with regard to the throwing method of fiber of the hollow structure of record in the above-mentioned patent documentation 1, for the lightweight of fiber, in the time of realizing high hollow rate, the technology of the polymer that spues from the hole fusion that spues of nozzle of needing to fit, operation is numerous and diverse.
In addition, Yi Bian keep the intensity of fiber, adopt hollow structure Yi Bian turn to purpose, so thermal insulation is low with light weight.Therefore, there is following shortcoming: when being used for dress material etc. carrying out blending, in needing the dress material of thermal insulation, be difficult to adopt.
In addition, with regard to the composite fibre of record in the above-mentioned patent documentation 2, also can be applied to require the dress material of taste, but have following shortcoming:, in the dress material that uses a large amount of fibers, be difficult to adopt owing to do not turn to purpose with light weight.
Patent documentation 1: TOHKEMY 2005-256243 communique
Patent documentation 2: No. 3356438 communique of Japan Patent
Summary of the invention
The objective of the invention is to, provide a kind of and show the fiber that sufficient metallic luster, light weight and thermal insulation are high and the effective manufacturing approach of this fiber as taste.
Method as being used to solve above-mentioned problem is described below.That is,
< 1>a kind of fiber is characterized in that, only constitutes by having crystalline polymer, has the cavity in inside.
< 2>like above-mentioned < 1>described fiber; L/r ratio when the average length that wherein, the average length in the said cavity on the thickness direction of differently-oriented directivity that is orthogonal to the cavity is set at the said cavity on the differently-oriented directivity in r (μ m), said cavity is set at L (μ m) is more than 10, below 100.
<3>As above-mentioned<1>～<2>In each described fiber, wherein, the cavity sectional area Y (μ m
2) with respect to sectional area X (the μ m of this fiber on the direction that is orthogonal to length direction
2) the average out to of ratio (Y/X) more than 0.05, below 0.4.
< 4>like each described fiber in above-mentioned < 1 >～< 3 >; Wherein, With the transmissivity of this fiber be set at M (%), by with the crystalline polymer phase of having of this fiber with have that crystalline polymer constitutes and transmissivity identical with the thickness of this fiber and that do not have a fiber in cavity when being set at N (%); The M/N ratio is below 0.2, and the glossiness of this fiber is more than 50.
< 5>like the fiber of each record in above-mentioned < 1 >～< 4 >; Wherein, The difference that the refractive index that the mean number in the cavity in the arbitrary section of thickness direction of the differently-oriented directivity that is orthogonal to the cavity is set at P, refractive index with crystalline polymer portion is set at N1, cavity is set at N2, N1 and N2 be set at Δ N (=N1-N2) time, the amassing of Δ N and P is more than 2.
< 6 >, wherein, have crystalline polymer and only constitute by a kind of like each described fiber in above-mentioned < 1 >～< 5 >.
< 7>like each described fiber in above-mentioned < 1 >～< 6 >, wherein, have crystalline polymer and be selected from TPO, polyesters and polyamide-based at least a kind.
< 8>like each described fiber in above-mentioned < 1 >～< 7 >; It is with only carrying out melt spinning by having the resin combination that crystalline polymer constitutes; With 10～2; The speed of 000m/min, and draft temperature is set at T (℃), this glass transition temperature with crystalline polymer be set at Tg (℃) time
(Tg-30)≤T≤(Tg+50)
The draft temperature T of expression (℃) stretching obtains.
< 9>like the manufacturing approach of each described fiber in above-mentioned < 1 >～< 8 >, it is characterized in that, comprise following operation:
The melt spinning operation, it will be only carries out melt spinning by having the resin combination that crystalline polymer constitutes;
Stretching process, it is with 10～2, the speed of 000m/min, and draft temperature is set at T (℃), this glass transition temperature with crystalline polymer be set at Tg (℃) time
(Tg-30)≤T≤(Tg+50)
The draft temperature T of expression (℃) stretch.
According to the present invention, can solve existing variety of issue, can provide as taste to show the fiber that sufficient metallic luster, light weight and thermal insulation are high and the effective manufacturing approach of this fiber.
Description of drawings
Fig. 1 be the expression fiber of the present invention manufacturing approach in spinning process one the example figure.
Fig. 2 be the expression fiber of the present invention manufacturing approach in stretching process one the example figure.
Fig. 3 A is the figure that is used to explain aspect ratio, is the stereogram of fiber.
Fig. 3 B is the figure that is used to explain aspect ratio, is the A-A ' sectional view of the fiber among Fig. 3 A.
Fig. 3 C is the figure that is used to explain aspect ratio, is the B-B ' sectional view of the fiber among Fig. 3 A.
Fig. 4 is the photograph image in cross section of the fiber of embodiment 1.
The specific embodiment
(fiber)
Fig. 1 is the sectional view that is orthogonal on the direction of length direction of fiber of the present invention.As shown in Figure 1, fiber 10 of the present invention has cavity 100 in inside.
< resin combination >
Above-mentioned resin combination forms with having crystalline polymer, as component of polymer, is merely this and has crystalline polymer, but as the composition beyond the polymer, also can comprise the adding ingredient of suitable selection as required.
As the shape of above-mentioned resin combination, not special restriction can suitably be selected according to purpose, for example, can enumerate for example membranaceous or sheet.
In addition,, can make composite,, also can the section of this resin combination inserted in other sheet and carried out integratedly, make resin combination as this instance with independent a kind or material more than 2 kinds as the structure of above-mentioned resin combination.
< < having crystalline polymer>>
Generally speaking, polymer can be divided into crystalline polymer and amorphism (amorphous) polymer.Above-mentioned crystalline polymer is not 100% crystallization usually, and is included in crystallinity zone that the molecule of long-chain shape in the molecular structure arranges regularly and the amorphous regions (amorphous) of not arranging regularly.
In the present invention, above-mentioned have crystalline polymer and in molecular structure, comprise above-mentioned crystallinity zone at least and get final product, and also can mix and have crystallinity zone and amorphous regions.
Has a crystalline polymer as above-mentioned; Not special restriction; Can suitably select according to purpose; For be selected from TPO, polyesters and polyamide-based at least a kind; For example can enumerate: polyolefin (for example, high density polyethylene (HDPE), polypropylene etc.), polyamide (PA) (for example nylon 6 etc.), polyacetals (POM), polyester (for example PET, PEN, PTT, PBT, PBN etc.), syndiotactic polytyrene (SPS), polyphenylene sulfide (PPS), polyether-ether-ketone (PEEK), liquid crystal polymer (LCP), fluororesin etc.Wherein, consider preferred polyester, syndiotactic polytyrene (SPS), liquid crystal polymer (LCP), more preferably polyester from the viewpoint of mechanical strength or manufacturing.In addition, also can or make its copolymerization and use the polyblend more than 2 kinds in these polymer.
As above-mentioned melt viscosity with crystalline polymer, not special restriction can suitably not selected according to purpose, preferred 50Pas～1,000Pas, more preferably 70Pas～750Pas, further preferred 80Pas～450Pas.Above-mentioned melt viscosity is 50Pas～1, and is during 000Pas, preferred aspect the dimensionally stable of the melt spinning that when melt spinning, spues from nozzle, the easy and uniform ground throwing.In addition, above-mentioned melt viscosity is 50Pas～1, during 000Pas, the viscosity when melt spinning be fit to and extrude easily or the diameter during throwing preferred aspect stable.
At this, above-mentioned melt viscosity can utilize for example board-like flow graph, capillary rheometer to measure.
As the not special restriction of above-mentioned inherent viscosity (IV:IntrinsicViscosity) with crystalline polymer, can suitably select according to purpose, preferred 0.4～1.5, more preferably 0.6～1.2, further preferred 0.7～1.0.Above-mentioned IV is 0.4～1.5 o'clock, and the tensile strength of the silk of processing raises, and can stretch effectively.
At this, above-mentioned IV for example can utilize Ubbelohde viscometer to measure.
As above-mentioned fusing point (Tm) with crystalline polymer, not special restriction can be selected according to purpose, and preferred 40 ℃～350 ℃, more preferably 100 ℃～300 ℃, further preferred 150 ℃～260 ℃.When above-mentioned fusing point is 40 ℃～350 ℃, keep easily diametrically preferred in the temperature range of in common use, being predicted, needed special technique, also preferred aspect the throwing equably in the processing under special use high temperature.
At this, above-mentioned fusing point for example can utilize differential thermal analysis device (DSC) to measure.
As above-mentioned weight average molecular weight with crystalline polymer, not special restriction can suitably not selected according to purpose, and is preferred 5,000～1,000,000, and more preferably 10,000～800,000, further preferred 15,000～700,000.Above-mentioned weight average molecular weight is 5,000 when following, worries fracture when stretching; Above-mentioned weight average molecular weight is 1,000,000 when above; Might be difficult to stretch, also be difficult to manifest the cavity even worry to stretch, when it is 15; 000～700,000 o'clock, preferred in manifesting aspect easy property balanced of the easy property of drawing process and cavity.
At this, above-mentioned weight average molecular weight for example can utilize gel permeation chromatography (GPC Gel Permeation Chromatography) to measure.
-mylar-
At this, have in the crystalline polymer above-mentioned, consider from the viewpoint of mechanical strength or manufacturing, the mylar that especially preferably uses is in the present invention described.
Above-mentioned mylar is with the polymer of ester bond as the main key chain of main chain.Therefore; As being suitable as above-mentioned above-mentioned polyester with crystalline polymer; Not only comprise above-mentioned illustrative PET (PETG), PEN (PEN), PTT (polytrimethylene terephthalate), PBT (polybutylene terephthalate (PBT)), PBN (PBN), but also all comprise the macromolecular compound that the polycondensation reaction through dicarboxylic acids composition and diol component obtains.
As above-mentioned dicarboxylic acids composition, not special restriction can suitably be selected according to purpose, for example can enumerate: aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, hydroxyl carboxylic, polyfunctional acid etc., wherein, the optimization aromatic dicarboxylic acids.
As above-mentioned aromatic dicarboxylic acid; For example can enumerate: terephthalic acid (TPA), M-phthalic acid, diphenyldicarboxylic acid, diphenyl sulfone dicarboxylic acids, naphthalene dicarboxylic acids, biphenoxyl ethane dicarboxylic acids, 5-sodium sulfo isophthalate etc.; Preferred terephthalic acid (TPA), M-phthalic acid, diphenyldicarboxylic acid, naphthalene dicarboxylic acids, more preferably terephthalic acid (TPA), diphenyldicarboxylic acid, naphthalene dicarboxylic acids.
As above-mentioned aliphatic dicarboxylic acid, for example can enumerate: oxalic acid, butanedioic acid, arachic acid, adipic acid, decanedioic acid, dimeric dibasic acid, dodecanedioic acid, maleic acid, fumaric acid.As above-mentioned alicyclic dicarboxylic acid, for example can enumerate: cyclohexyne dicarboxylic acids etc.As above-mentioned hydroxy acid, for example can enumerate: P-hydroxybenzoic acid etc.As above-mentioned polyfunctional acid, for example can enumerate: trimellitic acid, PMA etc.
As above-mentioned diol component, not special restriction can suitably be selected according to purpose, for example can enumerate: aliphatic diol, alicyclic diol, aromatic diol, diethylene glycol, PAG etc., wherein, the aliphatic glycol.
As above-mentioned aliphatic diol, for example can enumerate: ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, neopentyl glycol, triethylene glycol etc., wherein, preferred especially propylene glycol, butanediol, pentanediol, hexylene glycol.As above-mentioned alicyclic diol, can enumerate for example cyclohexanedimethanol etc.As above-mentioned aromatic diol, can enumerate for example bisphenol-A, bisphenol S etc.
As the melt viscosity of above-mentioned mylar, not special restriction can suitably not selected according to purpose, preferred 50Pas～700Pas, more preferably 70Pas～500Pas, further preferred 80Pas～300Pas.The big side of above-mentioned melt viscosity manifests the cavity easily when stretching, when above-mentioned melt viscosity is 50Pas～700Pas, when melt spinning, extrude easily, or resin flow is stable and be difficult for being detained, and is preferred aspect stay in grade.In addition, when above-mentioned melt viscosity is 50Pas～700Pas, when stretching, suitably keep tensile stress, so easy and uniform ground stretches, preferred aspect easy fracture not.And when above-mentioned melt viscosity was 50Pas～700Pas, the form of the melt spinning that when melt spinning, spues from nozzle was kept easily, can stably be shaped, or goods cracky etc. not, preferred aspect the rerum natura rising.
As the inherent viscosity (IV) of above-mentioned mylar, not special restriction can suitably not selected according to purpose, and is preferred 0.4～1.2, and more preferably 0.6～1.0, further preferred 0.7～0.9.The side that above-mentioned IV is big manifests the cavity easily when stretching, above-mentioned IV is 0.4～1.2 o'clock, when melt spinning, extrude easily, or resin flow is stablized and difficult the delay, and is preferred aspect stay in grade.In addition, above-mentioned IV is 0.4～1.2 o'clock, even when melt spinning, be provided with under the situation of filter of molten resin, also is difficult for applying load to filter, and is stable and be difficult for taking place aspect the delay preferred in resin flow.And above-mentioned IV is 0.4～1.2 o'clock, when stretching, suitably keeps tensile stress, and therefore, easy and uniform ground stretches, and is being difficult for applying aspect the load preferred to device.In addition, above-mentioned IV is 0.4～1.2 o'clock, and is not preferred aspect cracky, the rerum natura rising at goods.
As the fusing point of above-mentioned mylar, not special restriction can suitably be selected according to purpose, but consider from viewpoints such as heat resistance or throwing property, and preferred 150 ℃～300 ℃, more preferably 180 ℃～270 ℃.
Need to prove; As above-mentioned mylar; Can carry out polymerization and form polymer with a kind of above-mentioned dicarboxylic acids composition and above-mentioned diol component respectively, also can carry out copolymerization and form polymer with above-mentioned dicarboxylic acids composition and/or above-mentioned diol component more than 2 kinds.In addition, as above-mentioned mylar, also can the mixed with polymers more than 2 kinds be used.
In the mixing of above-mentioned polymer more than 2 kinds; The main relatively polymer that polymer added; In system during film or aspect rerum natura raise, extruded easily when melt extruding, preferred above-mentioned relatively main polymer, melt viscosity and inherent viscosity are approaching, addition is a small amount of.
In addition, with the radioparent control of improvement, light of the flow behavior of above-mentioned polyester, with the raising of the adaptation of coating fluid etc. be purpose, can add the resin beyond the polyester system to above-mentioned mylar.
Like this, be that particulate, immiscible cavities such as resin form agent even fiber of the present invention does not add added in the prior art inorganic especially, also can form the cavity with easy operation.And, need not be used for making inert gas dissolve in the special devices of resin in advance yet.Need to prove, state after carrying out about the manufacturing approach of fiber.
At this,, then can contain other composition as required if fiber of the present invention is the composition that manifests that is helpless to the cavity.As above-mentioned other composition, can enumerate: filler, heat-resisting stabilizing agent, anti-oxidant, ultra-violet absorber, organic lubricant, nucleator, dyestuff, pigment, fire retardant, releasing agent, dispersant, coupling agent etc.Whether above-mentioned other composition helps manifesting of cavity, can be used in the cavity or whether empty interface portion can detect the composition (each that state for example, becomes to grade) that has beyond the crystalline polymer and differentiate.
As above-mentioned anti-oxidant, not special restriction can suitably be selected as required.For example can enumerate: phenol system compound, chalcogenide compound, phosphorus series compound.Wherein, can enumerate known hindered phenol.As above-mentioned hindered phenol, for example can enumerate with イ Le ガ ノ Star Network ス 1010, with ス ミ ラ イ ザ one BHT, with commercially available anti-oxidants of trade name such as ス ミ ラ イ ザ one GA-80.
In addition, also can with above-mentioned anti-oxidant as anti-oxidant, further make up secondary antioxidant and use.As above-mentioned secondary antioxidant, for example can enumerate with ス ミ ラ イ ザ one TPL-R, with ス ミ ラ イ ザ one TPM, with trade names such as ス ミ ラ イ ザ one TP-D commercially available anti-oxidant.
As above-mentioned releasing agent; Can enumerate animals such as department of botany's wax, beeswax, lanolin such as Brazil wax is that mineral such as wax, montan wax are that oil such as wax, paraffin, Tissuemat E are that greases such as wax, castor oil and derivative thereof, aliphatic acid and derivative thereof are wax; As advanced higher fatty acid derivative, can enumerate the ester of the above alcohol of higher fatty acids such as laurate, stearic acid, montanic acid and monobasic or binary etc.
As above-mentioned fire retardant, not special restriction can suitably be selected according to purpose, but preferred especially bromide fire retardant.As bromide fire retardant, can use organic halogenated flame retardants such as HMW organic halogen compound, low molecular weight organic halogen compound separately, also can be also with more than 2 kinds.In addition, also can use fire retardants such as phosphorus system, inorganic system.
< cavity >
Fiber of the present invention has the cavity, on the aspect ratio in above-mentioned cavity, has characteristic.
Above-mentioned cavity is meant the zone of the vacuum state that is present in resin-formed body inside or the zone of gas phase.
Fig. 3 A～3C is the figure that is used to explain aspect ratio, and Fig. 3 A is the stereogram of fiber of the present invention, and Fig. 3 B is the A-A ' sectional view of the fiber of the present invention among Fig. 3 A, and Fig. 3 C is the B-B ' sectional view of the fiber of the present invention among Fig. 3 A.
Above-mentioned aspect ratio be meant with surperficial 10a that is orthogonal to fiber 10 of the present invention and the average length that is orthogonal to the cavity 100 on the direction of differently-oriented directivity in above-mentioned cavity be set at r (μ m) (with reference to Fig. 3 B), L/r ratio when the average length that is orthogonal to the cavity 100 on the differently-oriented directivity in surface and above-mentioned cavity of fiber of the present invention is set at L (μ m) (with reference to Fig. 3 C).
As above-mentioned aspect ratio, only otherwise damage effect of the present invention, just not special the qualification can suitably be selected according to purpose, is preferably 10 or more below 100, and be more preferably more than 15 below 100, further preferred more than 20 below 90.
During above-mentioned aspect ratio less than 10, reflectivity descends sometimes, and when it surpassed 100, thermal insulation descended sometimes, causes that mechanical characteristic descends.Above-mentioned aspect ratio is more than 10,100 when following, aspect reflection, various performances such as heat insulation and mechanical characteristic balanced, be favourable.
< transmittance of fiber >
The transmittance of so-called fiber; As the term suggests be meant the transmission of the outward appearance of seeing when the collection of filaments become clothes etc.; With the transmissivity of resin combination be set at N (%), the optical transmission rate of imaginary plane during with respect to the plane of making the boundling fiber is set at M (%), calculates the M/N ratio.
Above-mentioned M/N ratio does not have special restriction, can suitably select according to purpose, and is preferred below 0.2.More preferably below 0.19, further preferred below 0.18.
When above-mentioned M/N ratio surpassed 0.2, reflectivity reduced sometimes, and the impression of the outward appearance of seeing when processing fiber descends.
Need to prove that above-mentioned transmissivity for example can utilize spectrophotometer to measure.
< glossiness of fiber >
The glossiness of so-called fiber is as the term suggests be meant the glossiness of the outward appearance of seeing when the collection of filaments become clothes etc.
The not special restriction of above-mentioned glossiness can suitably be selected according to purpose, and is preferred more than 50, more preferably more than 60, further preferred more than 70, preferred especially more than 90.
At this, above-mentioned glossiness for example can utilize goniophotometer to measure.
Need to prove, the differently-oriented directivity in so-called above-mentioned cavity, stretching be merely single shaft to situation under, represent the draw direction (first draw direction) of this single shaft.Usually, owing to indulge stretching along the flow direction of formed body during fabrication, therefore, this vertical direction that stretches is equivalent to the differently-oriented directivity (first draw direction) in above-mentioned cavity.
In addition, be stretched as twin shaft under above situation, expression forms at least one direction in the draw direction of purpose with the cavity.Usually, though at twin shaft in above stretching, also indulge stretching along the flow direction of formed body during fabrication, and can form the cavity by this vertical stretching, therefore, the direction of this vertical stretching is equivalent to the differently-oriented directivity (first draw direction) in above-mentioned cavity.
< occupied area in cavity >
In addition, with regard to fiber of the present invention, the sectional area of the fiber in the arbitrary section that is orthogonal to its length direction is set at X (μ m
2), the sectional area in the cavity in the above-mentioned cross section is set at Y (μ m
2) time, preferably the ratio (Y/X) of these sectional areas is more than 0.05, below 0.4.
Need to prove that each sectional area in the above-mentioned cross section can utilize the image of light microscope or electron microscope to measure.
In addition, fiber of the present invention has characteristic amassing of the mean number P in the cavity of film thickness direction, the refractive indices N with crystalline polymer portion and cavity and above-mentioned Δ N and above-mentioned P.
The number in the cavity of above-mentioned film thickness direction is meant, at the surperficial 10a that is orthogonal to fiber 10 of the present invention and comprise in the face (A-A ' cross section among Fig. 3 A) of the direction of the differently-oriented directivity that is orthogonal to above-mentioned cavity the number in the cavity 100 that film thickness direction comprised.
In addition, above-mentioned have crystalline polymer portion and be meant the part (by having the part that crystalline polymer constitutes) in above-mentioned fiber beyond the cavity.
As the mean number P in the cavity of above-mentioned film thickness direction, only otherwise damage effect of the present invention, just not special restriction can suitably be selected according to purpose, and is preferred more than 5, more preferably more than 10, further preferred more than 15.
At this, the number in the cavity of above-mentioned film thickness direction can utilize the image of light microscope or electron microscope to measure.
Above-mentioned refractive indices N with crystalline polymer portion and cavity specifically is meant, when the refractive index that above-mentioned refractive index with crystalline polymer portion is set at N1, cavity is set at N2, as the Δ N of the difference of N1 and N2 (=N1-N2) value.
At this, refractive index N1, N2 with crystalline polymer portion or cavity can utilize Abbe refractometer etc. to measure.
Above-mentioned Δ N and above-mentioned P long-pending only otherwise damage effect of the present invention, just not special restriction can suitably be selected according to purpose, and is preferred more than 2, more preferably more than 2.5, further preferred more than 3.
During the long-pending less than 2 of above-mentioned Δ N and above-mentioned P, reflectivity descends or thermal insulation descends sometimes.
Like this, fiber of the present invention has above-mentioned cavity through portion within it, has the characteristic of various excellences at for example aspect such as reflectivity or glossiness.In other words, the metamorphosis in the cavity of the inside through making fiber of the present invention can the accommodation reflex rate or characteristic such as glossiness.
Because fiber of the present invention has above-mentioned cavity, and do not add that being used to of being added in the prior art manifest the cavity inorganic be particulate, immiscible resin etc. or inert gas, therefore, have excellent surface smoothing property.
As the surface smoothing property of fiber of the present invention, not special restriction can suitably be selected according to purpose, but below the preferred 0.3 μ m of surface roughness (Ra), further below the preferred 0.25 μ m, below the preferred especially 0.1 μ m.
< manufacturing approach of fiber of the present invention >
As the manufacturing approach of fiber of the present invention, comprise at least resin combination is carried out the melt spinning operation of melt spinning and the stretching process that this resin combination of institute's spinning is stretched, and then comprise other operations such as film making process as required.
Need to prove,, form with having crystalline polymer as the material of above-mentioned resin combination; As component of polymer; Be merely this and have crystalline polymer, but, also can contain the adding ingredient of suitably selecting as required as the composition beyond the polymer.
In addition, as the structure of above-mentioned resin combination, as long as its inside is not formed with the cavity, just not special restriction can suitably be selected according to purpose.
In addition, as the shape of above-mentioned resin combination, not special restriction can suitably be selected according to purpose, can enumerate for example membranaceous or sheet etc.
< < dissolving spinning process>>
Above-mentioned melt spinning operation is that above-mentioned resin combination is extruded and processed fibrous operation from the nozzle that is formed with many apertures, as spinning process, can enumerate for example melt spinning, wet type spinning, dry spinning etc., wherein, and the preferred molten spinning.
Above-mentioned melt spinning is a material of processing the thick liquid nano of high temperature with making the polymer heating and melting, spinning and stretch, make its curing and process the operation of fiber in the atmosphere (being generally cold air) of cold.Compare with wet type spinning or dry spinning, operation is easy, and spinning speed also can especially be accelerated, but is limited to the polymer in about fusion below 300 ℃ such as polyester, nylon, polypropylene, PBT, PTT, PLA.
In the spinning process in the present invention,, therefore, be set at the operation of making undrawn yarn (UDY:undrawn yarn) owing to carry out the stretching of the resin combination of spinning in as the stretching process of back operation.At this, undrawn yarn is meant the shape that presents fiber but the degree of orientation of strand is low, can easily be stretched to 3 times～4 times and non-restoring silk, usually with 2, and the spinning speed manufacturing below about 000m/ minute.
< < stretching process>>
As shown in Figure 2; The precursor 21 that becomes through the melt spinning that will as above-mentioned, obtain for example inserts in the heating furnace 30 that is adjusted into 25 ℃～150 ℃, add the rotary speed difference of niprolls 41 and 42 and give tensile stress and stretch; Cause constriction, make fiber thus with cavity.According to circumstances, even remove heating furnace, only niproll is heated (25～150 ℃), also can make same fiber of the present invention 10.31 expression annealing in process stoves among Fig. 2,32 expression coiler devices.
Particularly, the above-mentioned resin combination (undrawn yarn) that is spun to carries out uniaxial tension at least.And, utilize above-mentioned stretching process, in the stretching resin composition, portion's formation within it is the cavity of major axis with first draw direction, obtains fiber 10 of the present invention thus.
Form the reason in cavity as utilizing to stretch; Can think; At least a phase with the crystallization that is difficult to extend when crystalline polymer stretches to be included in that constitutes above-mentioned resin combination, the shape that is torn with the resin between hard crystallization are peeled off stretching; Thus, it becomes empty formation source and forms the cavity.
Need to prove that it is that a kind of situation but also the situation that has crystalline mixed with polymers or copolymerization more than two kinds are also passable that the cavity formation that this stretching causes not only has crystalline polymer.
Generally speaking, in stretching, can utilize the combination of roller or the speed difference between roller to regulate vertical hop count or the draw speed that stretches.
At this, above-mentioned constriction be meant the necking down shape distortion that above-mentioned polymer moulded bodies produces when stretching (with reference to macromolecule engineering lecture 6 plastics formings processing macromolecule association compile, the distribution of people academy, clear and first edition distribution on April 25th, 41).In addition, on one side will be when above-mentioned stretching, the above-mentioned polymer moulded bodies necking down on one side phenomenon being out of shape, sharply reducing in the necking section cross section is defined as " constriction manifests ".
--draw speed--
As the draw speed of above-mentioned vertical stretching, only otherwise damage effect of the present invention, just not special restriction can suitably be selected according to purpose; Preferred 10m/min～2,000m/min, more preferably 15m/min～1; 000m/min, further preferred 20m/min～1,000m/min.Above-mentioned draw speed is 10m/min when above, manifest easily aspect the sufficient constriction preferred.In addition, above-mentioned draw speed is 2, when 000m/min is following, stretch uniformly easily, silk easy fracture not, need not be the large-scale stretching device of purpose with the high-speed stretch, preferred especially aspect can reducing cost.
--draft temperature--
Temperature when stretching, not special restriction can suitably not selected according to purpose, but draft temperature is set at T (℃), glass transition temperature be set at Tg (℃) time, preferably exist
(Tg-30)≤T≤(Tg+50)
The expression scope draft temperature T (℃) under stretch, more preferably exist
(Tg-25)≤T≤(Tg+45)
The expression scope draft temperature T (℃) under stretch, further preferably exist
(Tg-20)≤T≤(Tg+40)
The expression scope draft temperature T (℃) under stretch.
Generally speaking; Draft temperature (℃) high more, tensile stress also is suppressed lowly more, can easily stretch; But above-mentioned draft temperature (℃) be below glass transition temperature (Tg)+50} ℃ the time, raise at the volume ratio that forms the cavity, aspect ratio is preferred aspect reaching more than 10 easily.In addition, above-mentioned draft temperature (℃) be more than glass transition temperature (Tg)-30} ℃ the time, and manifest fully aspect empty preferred.
At this, above-mentioned draft temperature T (℃) can utilize for example contactless thermometer to measure.In addition, above-mentioned glass transition temperature Tg (℃) for example can utilize differential thermal analysis device (DSC) to measure.
Need to prove that in above-mentioned stretching process, the resin combination after the stretching also can be with the further heating and make it carry out thermal contraction or apply processing such as tension force of purposes such as dimensionally stableization.
In addition, the manufacturing of above-mentioned resin combination can be carried out with above-mentioned stretching process independently, also can carry out continuously.
Embodiment
Below, embodiments of the invention are described, but the present invention does not receive any qualification of following embodiment.
(embodiment 1)
The making of-resin combination (undrawn yarn)-
Utilize the inherent viscosity (IV) of determination of ubbelohde viscometer polybutylene terephthalate (PBT) 100% resin PBT1 (in Fuji Photo Film Co., Ltd., making), the result is 0.8.
Use melt spinning machine under 245 ℃, to extrude above-mentioned PBT1, obtain resin combination (undrawn yarn) from nozzle.
-stretching process-
Then, with resulting (undrawn yarn) under 45 ℃ heating atmosphere, carry out uniaxial tension (multiplying power: 5 times), after confirming to have produced constriction, with speed edge and the initial equidirectional of 200m/min, make fiber with identical multiplying power with the speed of 200m/min.
1,500 times cross-section photograph of the fiber of the embodiment that processes 1 is shown in Fig. 4.Can confirm the cavity is arranged from this Fig. 4 at fibrous inside.
(embodiment 2)
The making of-resin combination (undrawn yarn)-
Operate equally with embodiment 1, measure the inherent viscosity (IV) of polybutylene terephthalate (PBT) 100% resin PBT2 (in Fuji Photo Film Co., Ltd., making), the result is 1.0.
Use melt spinning machine under 260 ℃, to extrude above-mentioned PBT2, obtain resin combination (undrawn yarn) from nozzle.
Then, resulting resin combination (undrawn yarn) under 50 ℃ heating atmosphere, carry out uniaxial tension (multiplying power: 5.5 times) with the speed of 300m/min, is made fiber.
(embodiment 3)
The making of-resin combination (undrawn yarn)-
Operate equally with embodiment 1, measure the inherent viscosity (IV) of PETG 100% resin PET1 (in film Co., Ltd. of Fuji, making), the result is 0.67.
With the PBT1 that uses among the embodiment 1 and above-mentioned PET1 by PBT1: PET1=90: 10 mix, and its mixture use melt spinning machine is extruded from nozzle under 285 ℃, obtain resin combination (undrawn yarn).
Then, make the draft temperature among the embodiment 1 change to 60 ℃, draw speed is substituted by 250m/min and (the vertical stretching that resulting resin combination (undrawn yarn) is stretched by 45 ℃; Multiplying power: 5 times); In addition, operate equally, make fiber with embodiment 1.
(comparative example 1)
The making of-fiber-
As comparative example 1,, make fiber based on the record of the embodiment 2 of TOHKEMY 2005-256243 communique.
(comparative example 2)
The making of-fiber-
As comparative example 2,, make fiber based on the record of the embodiment F-1 of No. 3356438 communiques of Japan Patent.
(comparative example 3)
The making of-fiber-
As comparative example 3, use the polymer identical with embodiment 2, draft temperature is changed to 50 ℃, under 100 ℃, stretch, in addition, operate the making fiber equally with embodiment 2.
To the fiber of in embodiment 1～3 and comparative example 1～3, processing, be summarized in table 1 expression.
[table 1]
In the table 1, "-" expression is not measured.
Comparative example 1 is the fiber with hollow structure and gap structure.
Comparative example 2 is the fibers with cavity.
Comparative example 3 is to use and identical materials of the present invention, but owing to changed draft temperature, therefore, for not producing the fiber in cavity.
Then, to the fiber of the foregoing description 1～3 and comparative example 1～3, estimate as follows.To measure the result and be shown in table 2, evaluation result will be shown in table 3.
< mensuration of the occupied area in cavity >
< < sectional area ratio in cavity>>
Use the photo of the section S EM of core layer to carry out image and handle, use all cavities to obtain the long-pending sectional area with blank part of global sections respectively, calculate the sectional area ratio in cavity, estimate.
< mensuration of transmissivity >
Use spectrophotometer (U-4100, Hitachi's system) to measure transmissivity N (%).Make light incident from the normal to a surface direction of above-mentioned resulting resin combination 5 degree that tilt, with the light intensity of this resin combination of transmission with the blank value of this resin combination transmission is compared.Wavelength uses 550nm.
In addition, resulting fiber is also operated with the mensuration of the transmissivity of above-mentioned resin combination equally, measured transmissivity M (%).
Need to prove,,, the transmissivity of above-mentioned resin combination is scaled with the identical size of thickness (diameter of section) of fiber calculates according to the rule of Lambert-Beer to the ratio (M/N) of the transmissivity of the transmissivity of above-mentioned resin combination and fiber.
< mensuration of glossiness >
(A) making of sample board
About 0.3g sample is carried out combing and doubling abreast with comb to fiber, on one side with sample all by being pressed on 4.5cm square the black clearer board, be arranged in parallel on one side, so that the surface is evenly neat.
(B) measure
Sample board is placed on the turntable of Pu Lulihe photometer (プ Le リ Star ヒ ホ ト メ one タ one); Compress with the switch frame; The direction of the fiber during with the position of turntable deflection δ=0 degree is installed towards the mode of light source one side, at opposite side installation code white plate.Filter uses L2, and (the center of gravity wavelength 540～550nm) of filter is measured anglec of rotation δ is set at 0 the brightness H1 of brightness H0 when being set at the anglec of rotation 22.5 and spending when spending.
(C) calculate
Obtain glossiness θ with following formula, represent with 2 times mean value.
Glossiness θ=(H1/H0) * K δ
At this, H0 is the brightness in a reference value (δ=0 degree) at sample, and H1 is the brightness in the position of rotation (δ=22.5 degree) at sample, and K δ is the correction factor with respect to the gloss of standard white plate, is set at K δ (22.5 degree)=1.037.
< mensuration of aspect ratio >
With the surface that is orthogonal to fiber and cross section (with reference to Fig. 3 B) that is orthogonal to vertical draw direction and the surface that is orthogonal to above-mentioned fiber and cross section (with reference to Fig. 3 C) the use scanning electron microscope parallel with above-mentioned vertical draw direction with 300～3; 000 times suitable multiplying power is carried out microscopic examination, in above-mentioned each cross-section photograph, sets respectively and measures frame.This mensuration frame is set with the mode that comprises 50～100 cavities in its frame.
Then; Measure to measure the number in cavity contained in the frame, it is individual that the number that the number in the cavity that the mensuration frame (with reference to Fig. 3 B) in the cross section that is orthogonal to above-mentioned vertical draw direction is contained is set at the contained cavity of m, the mensuration frame (with reference to figure C) in the cross section parallel with above-mentioned vertical draw direction is set at n.
And, measure the length (r in contained per 1 cavity of the mensuration frame (with reference to Fig. 3 B) in the above-mentioned cross section that is orthogonal to vertical draw direction
i), its average length is set at r.In addition, measure the length (L in contained per 1 cavity of the mensuration frame (with reference to Fig. 3 C) in the parallel cross section of above-mentioned and vertical draw direction
i), its average length is set at L.
That is, r and L can represent with following (1) formula and (2) formula respectively.
r＝(∑r
i)/m...(1)
L＝(∑L
i)/n...(2)
And, calculate L/r, be set at aspect ratio.
< the average number P in the cavity of film thickness direction >
At first, utilizing scanning electron microscope to take is orthogonal to the surface of fiber and is orthogonal to the cross section of indulging draw direction.
And, in cross-section photograph, draw straight line along film thickness direction (from the bottom surface of fiber up to top), measure the number in the cavity that is connected with above-mentioned straight line.20 straight lines are carried out this operation, obtain mean value.
< refractive indices N>with crystalline polymer portion and cavity
Utilize Abbe refractometer to measure to have the refractive index N1 of crystalline polymer portion and the refractive index N2 in cavity, calculate its difference DELTA N (=N1-N2).
< evaluation of light weight >
The density of estimation fiber is estimated based on following metewand as the index of light weight.Suppose that blank part is an air.
[metewand]
◎: good
Zero: general
△: poor slightly
*: bad
< evaluation of reflectivity >
Use spectrophotometer (V-570, Japanese beam split system) and integrating sphere I LN-472, measure light reflectance, estimate based on following benchmark with the wavelength of 550nm.
[metewand]
◎: reflectivity is more than 80%
Zero: reflectivity is more than 65%
△: reflectivity is more than 50% and less than 65%
*: reflectivity less than 50%
< evaluation of heat insulating ability >
With regard to the evaluation of heat insulating ability, make braided fabric of the present invention, estimate based on following metewand by 5 skilled persons.
[metewand]
Zero: sense is to quite warm
△: feel to warm
*: no change
[table 2]
In the table 2, "-" expression is not measured.
[table 3]
In the table 3, "-" expression is because comparative example 1 and 2 can not be made braided fabric, so do not carry out the evaluation of heat insulating ability.
Aspect heat insulating ability, because comparative example 2 does not have the cavity, so heat insulating ability is obviously poor, because comparative example 1 is the fiber of hollow structure, so heat insulating ability descends all the more.State heat insulating ability that we can say the still air that is not hollow, makes the space is best.
As shown in table 3, confirm: the sufficient reflectivity that embodiment 1～3 shows as fiber shows the performance that light weight and heat insulating ability are excellent.
Possibility of its application on the industry
Fiber of the present invention and the fiber that utilizes the manufacturing approach of fiber of the present invention to make show the sufficient metallic luster as taste, and light weight and thermal insulation are high, therefore, can be preferred for various uses such as dress material.
Claims (8)
1. a fiber is characterized in that,
Only constitute, have the cavity in inside by having crystalline polymer,
Sectional area Y (the μ m in cavity
2) be orthogonal to sectional area X (the μ m of this fiber on the direction of length direction relatively
2) the average out to of ratio (Y/X) more than 0.05 below 0.4.
2. fiber according to claim 1, wherein,
The average length in the said cavity on the thickness direction of differently-oriented directivity that will be orthogonal to the cavity is set at r (μ m), when the average length in the said cavity on the differently-oriented directivity in said cavity is set at L (μ m), the L/r ratio is more than 10 below 100.
3. fiber according to claim 1, wherein,
The transmissivity with this fiber be set at M (%), by with the crystalline polymer phase of having of this fiber with have that crystalline polymer constitutes and transmissivity identical with the fiber number of this fiber and that do not have a fiber in cavity when being set at N (%); The M/N ratio is below 0.2, and the glossiness of this fiber is more than 50.
4. fiber according to claim 1, wherein,
The refractive index that the mean number in the cavity in the diametric arbitrary section of differently-oriented directivity that will be orthogonal to the cavity is set at P, will have a crystalline polymer portion be set at N1, with the refractive index in cavity be set at N2, with the difference of N1 and N2 be set at Δ N (=N1-N2) time, the amassing of Δ N and P is more than 2.
5. fiber according to claim 1, wherein,
Having crystalline polymer only is made up of a kind of.
6. fiber according to claim 1, wherein,
Have crystalline polymer and be selected from TPO, polyesters and polyamide-based at least a kind of material.
7. fiber according to claim 1, wherein,
Said fiber is with only carrying out melt spinning by having the resin combination that crystalline polymer constitutes; With 10～2; The speed of 000m/min, and draft temperature is set at T (℃), this glass transition temperature with crystalline polymer be set at Tg (℃) time
(Tg-30)≤T≤(Tg+50)
The draft temperature T of expression (℃) stretching obtains.
8. the manufacturing approach of a fiber is characterized in that,
Said fiber only constitutes and has the cavity in inside by having crystalline polymer, sectional area Y (the μ m in cavity
2) be orthogonal to sectional area X (the μ m of this fiber on the direction of length direction relatively
2) the average out to of ratio (Y/X) more than 0.05 below 0.4,
Said manufacturing approach comprises:
The melt spinning operation, it will be only carries out melt spinning by having the resin combination that crystalline polymer constitutes;
Stretching process, it is with 10～2, the speed of 000m/min, and draft temperature is set at T (℃), this glass transition temperature with crystalline polymer be set at Tg (℃) time
(Tg-30)≤T≤(Tg+50)
The draft temperature T of expression (℃) stretch.
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| JP2008-031017 | 2008-02-12 | ||
| JP2008031017A JP4977054B2 (en) | 2008-02-12 | 2008-02-12 | Fiber and method for producing the same |
| PCT/JP2009/051911 WO2009101889A1 (en) | 2008-02-12 | 2009-02-04 | Fiber and process for producing the same |
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| JP2010190304A (en) * | 2009-02-17 | 2010-09-02 | Fujifilm Corp | Heat insulating material |
| JP2012046831A (en) * | 2010-08-24 | 2012-03-08 | Fujifilm Corp | Spinning method and spinning apparatus |
| JP2012106451A (en) * | 2010-11-18 | 2012-06-07 | Fujifilm Corp | Carbon fiber reinforced resin composite and production method for the same |
| JP2012140721A (en) * | 2010-12-28 | 2012-07-26 | Fujifilm Corp | Raw yarn for producing void-containing yarn and void-containing yarn |
| JP5586452B2 (en) * | 2010-12-28 | 2014-09-10 | 富士フイルム株式会社 | Method for producing void-containing yarn |
| US10858762B2 (en) * | 2012-02-10 | 2020-12-08 | Kimberly-Clark Worldwide, Inc. | Renewable polyester fibers having a low density |
| EP3011086B8 (en) * | 2013-06-20 | 2018-11-14 | Synvina C.V. | Process for the preparation of a fiber, a fiber and a yarn made from such a fiber |
| WO2018123240A1 (en) * | 2016-12-27 | 2018-07-05 | リンテック株式会社 | Actuator and method for manufacturing same |
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| JP2000226737A (en) * | 1999-02-08 | 2000-08-15 | Toray Ind Inc | Conjugate fiber and its production |
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| JP3109768B2 (en) * | 1992-09-10 | 2000-11-20 | 株式会社クラレ | Degradable composite fiber |
| JP4100206B2 (en) * | 2003-03-17 | 2008-06-11 | 東レ株式会社 | Manufacturing method of composite fiber excellent in light weight |
| JP2006345920A (en) * | 2005-06-13 | 2006-12-28 | Toray Ind Inc | Stuffing |
| JP2008057082A (en) * | 2006-08-31 | 2008-03-13 | Toray Ind Inc | Method for producing polylactic acid monofilament |
| US8329287B2 (en) * | 2007-03-30 | 2012-12-11 | Fujifilm Corporation | Void-containing resin molded product, production method therefor, and reflective plate |
| WO2008129715A1 (en) * | 2007-03-30 | 2008-10-30 | Fujifilm Corporation | Void-containing resin molded product, process for producing the void-containing resin molded product, and image receiving film or sheet for sublimation transfer recording material or thermal transfer recording material |
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| JP2000226737A (en) * | 1999-02-08 | 2000-08-15 | Toray Ind Inc | Conjugate fiber and its production |
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| JP2009191382A (en) | 2009-08-27 |
| WO2009101889A1 (en) | 2009-08-20 |
| CN101946031A (en) | 2011-01-12 |
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