CN101096784B - method for production of polyoxymethylene resin fiber - Google Patents
method for production of polyoxymethylene resin fiber Download PDFInfo
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- CN101096784B CN101096784B CN2007101263184A CN200710126318A CN101096784B CN 101096784 B CN101096784 B CN 101096784B CN 2007101263184 A CN2007101263184 A CN 2007101263184A CN 200710126318 A CN200710126318 A CN 200710126318A CN 101096784 B CN101096784 B CN 101096784B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
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Abstract
The invention provides a process for efficient production of untrafine-denier fibers which are made of polyoxymethylene resin and have various excellent characteristics. A process for the production of polyoxymethylene resin fibers which comprises conjugate-spinning both a polyoxymethylene resin which contains specific oxyalkylene units in an amount of 1.5 to 8.0mol per 100 mol of oxymethylene repeating units and has a melt index (as determined at 190 DEG C under a load of 2160g) of 1 to 120g/10min and a thermoplastic resin selected from among alkali-decomposable resins, resins soluble in water, and resins soluble in organic solvents and subjecting the obtained conjugated fibers to treatment with an alkali, water, or an organic solvent to remove the thermoplastic resin through decomposition or dissolution and thus form polyoxymethylene resin fibers.
Description
Technical field
The present invention relates to contain the manufacture method of the superfine fibre of acetal resin.
Background technology
As resin system superfine fibre is known the superfine fibre that contains mylar, polyamide, vistanex etc. arranged.As its manufacture method, proposed other resin compounded spinning that these resins and dissolubility decomposability etc. are different form have the composite fibre of island structure after, make the composition dissolving or the decomposition that form extra large structure, acquisition contains method (the Japanese Patent Publication 44-18369 communique of the superfine fibre of the composition that forms island structure, Japanese Patent Publication 47-37648 communique, Japanese Patent Publication 48-28005 communique, Japanese kokai publication sho 52-88619 communique, Japanese kokai publication sho 52-88622 communique, Japanese kokai publication sho 55-128038 communique, Japanese kokai publication hei 5-71006 communique).The particulate filter effect height of this superfine fibre, be used in filter cloth, air filter, copy in the industry material of slurry with filtration applications such as canvas.In addition, used uniformity height, the density height of Wet-laid non-woven fabric of the staple fibre of superfine fibre, can obtain order and pay filter very low, that filtering function is very high, various application in the industry purposes therefore wait in expectation.
But the performance such as restorative that contains alkali resistance, hydrolytic resistance, solvent resistance, intensity, the elongation strain of the superfine fibre of these resins may not be abundant, must these characteristics utilize in the field, can not satisfy its requirement.
Relative therewith, excellence such as the solvent resistance of acetal resin, alkali resistance, hydrolytic resistance, intensity, elongation of fiber are restorative enjoys expectation as the fiber than fiber higher functions such as polyester, polyamide, polyolefin with material.
Yet the crystallization degree height and the crystallization speed of acetal resin are fast, so its melt spinning or stretch process obviously be worse than other resin, and for example above-mentioned mylar, polyamide, vistanex etc. are very difficult to be processed into fiber.Therefore, manufacturing for superfine fibre, though in above-mentioned Japanese Patent Publication 44-18369 communique, Japanese Patent Publication 47-37648 communique, Japanese Patent Publication 48-28005 communique, Japanese kokai publication sho 52-88619 communique, Japanese kokai publication sho 52-88622 communique, Japanese kokai publication sho 55-128038 communique, Japanese kokai publication hei 5-71006 communique etc., disclose the manufacturing of the superfine fibre that contains mylar, polyamide, vistanex etc., do not mentioned fully for the superfine fibre that contains acetal resin.
Therefore, because acetal resin has excellent many characteristics, its superfine fibre is expected in the multiple use that with the industry purposes is the center, therefore urgent efficient, the economic manufacture method of wishing to develop the superfine fibre that contains acetal resin.
Summary of the invention
The objective of the invention is to address the above problem, the superfine fibre with excellent many characteristics that contains acetal resin is provided, the good manufacture method of production efficiency of spinnability, draftability excellence is provided.
The inventor etc. are in order to reach above-mentioned purpose, further investigate, found that the specific polyacetal copolymer of having controlled the crystallization characteristic by use, it is good that spinnability and draftability become, in the manufacturing of the superfine fibre that contains acetal resin, utilize composite spinning method very preferably to bring into play effect etc., and then finished the present invention.
Promptly, the present invention is the manufacture method of polyoxymethylene resin fiber, it is characterized in that, every 100mol formaldehyde repetitive is contained oxyalkylene units shown in the following general formula (1) of 1.5～8.0mol, (190 ℃ of melt index (MI)s, loading 2160g) be 1～120g/10 minute acetal resin (A) be selected from alkali decomposability resin (B-1), after thermoplastic resin (B) composite spinning of water-soluble resin (B-2) and organic solvent soluble resin (B-3) prepares composite fibre, this composite fibre is carried out alkali treatment, water treatment or organic solvent are handled, and thermoplastic resin (B) is decomposed to remove or dissolve remove.
(in the formula, R
1, R
2Be selected from the alkyl of hydrogen, carbon number 1～8, the organic group with alkyl of carbon number 1～8, phenyl, have the organic group of phenyl, R
1, R
2Can be the same or different.M represents 2～6 integer.)
Can make the superfine fibre that contains acetal resin, has excellent many characteristics efficiently by the present invention.
The composite spinning method that utilizes among the present invention is characterised in that, will follow the spinnability of the high crystallization degree of acetal resin, high crystallization speed, the shortcoming of draftability to relax.
In addition, the alkali resistance of acetal resin, solvent resistance excellence, therefore also has following feature: the composite spinning pairing resin in making as the superfine fibre that has utilized composite spinning, can from alkali decomposability resin, water-soluble resin, solvent soluble resin etc., select pairing resin choice wide ranges widely.And the intersolubility shortcoming of acetal resin and other resins has been brought into play effect effectively, is difficult to dissolve each other with the pairing resin in composite spinning, has stably formed the fibrous unit that contains acetal resin.
Summary of the invention
Below explain the present invention.
The present invention as mentioned above, has following feature, after specific acetal resin (A) and alkali decomposability resin (B-1), water-soluble resin (B-2) or organic solvent soluble resin (B-3) composite spinning prepared composite fibre, this composite fibre is carried out alkali treatment, water treatment or organic solvent to be handled, alkali decomposability resin (B-1), water-soluble resin (B-2) or organic solvent soluble resin (B-3) decomposed to remove or dissolve remove, obtain polyoxymethylene resin fiber.
The specific acetal resin (A) that uses among the present invention is to contain the polyacetal copolymer that every 100mol formaldehyde unit is an oxyalkylene units shown in the above-mentioned general formula of 1.5～8.0mol (1) in the polymer chain that mainly contains the formaldehyde repetitive.Be preferably the polyacetal copolymer that every 100mol formaldehyde unit contains oxyalkylene units shown in 1.5～5.0mol general formula (1), be preferably the polyacetal copolymer that every 100mol formaldehyde unit is an oxyalkylene units shown in the above-mentioned general formula of 2.0～4.0mol (1) especially.
General formula (1) if shown in the ratio of oxyalkylene units tail off, then the crystallization speed of polyacetal copolymer accelerates, not only the broken string in utilizing the fiber manufacturing process of composite spinning usually takes place, and the crystallization degree increase after the spinning end just, so draftability also has the tendency of reduction.On the contrary, if the ratio of oxyalkylene units is too much, then intensity of fiber etc. becomes insufficient.
The acetal resin that uses among the present invention (A) is 1～120g/10 minute according to ASTMD-1238, the melt index (MI) (MI) measured under 190 ℃, 2160g loading preferably, is preferably 2.5～100g/10 minute, more preferably 5.0～90g/10 minute.
The excessive person of melt index (MI) (MI) therefore is easy to break, makes unstable when spinning and stretching because acetal resin is a low molecular weight.In addition, during for the too small acetal resin of melt index (MI) (MI), because high viscosity, the load during spinning increases, and not only spinning becomes difficult, and tensile stress increases, and difficulty therefore stretches.
The manufacture method of the above-mentioned acetal resin (A) that uses among the present invention is not particularly limited, and as a rule can obtain with three alkane with as the cyclic ether compound of comonomer or the method for the block polymerization of cyclic formals compound by the main cationic polymerization catalyst that uses.Can use known devices such as discontinuous, continous mode as polyplant.
The importing ratio of the oxyalkylene units shown in the above-mentioned general formula (1) can be according to the amount adjustment of the comonomer of copolymerization, and the chain-transferring agent that melt index (MI) (MI) uses can be according to polymerization the time, for example addition adjustment such as dimethoxym ethane.
Cyclic ether compound or cyclic formals compound as the comonomer use, can enumerate ethylene oxide, propylene oxide, butylene oxide, styrene oxide, oxetanes, oxolane, trioxepan, 1,3-dioxolanes, propylene glycol formal, diethylene glycol formal, triethylene glycol formal, 1,4-butanediol formal, 1,5-pentanediol formal, 1,6-hexylene glycol formal etc., wherein preferred ethylene oxide, 1,3-dioxolanes, diethylene glycol formal, 1,4-butanediol formal.In addition, polyacetal copolymer can also have side chain or cross-linked structure.
By the polyacetal copolymer that polymerization obtains handle at the inactivation that has carried out catalyst, after the stabilization processes of the washing of the removing of unreacted monomer, polymer, drying, unstable terminal part etc., further utilize the stabilization processes of the known various stabilizing agents of cooperation etc., supply in practicality.As the stabilizing agent of representative, can enumerate the hydroxide, inorganic salts, carboxylate of fortified phenol compounds, nitrogen-containing compound, alkali or alkaline-earth metal etc.
And then, adding for thermoplastic resin in the acetal resin that can also use in the present invention in the scope of not damaging the object of the invention as required is common additive, colouring agent such as dyestuff, pigment for example, lubricant, nucleator, releasing agent, antistatic agent, surfactant or high-molecular organic material, more than a kind or 2 kinds of filler of inorganic or organically fibrous, tabular, powder shape etc.
Among the present invention, after above-mentioned acetal resin (A) and alkali decomposability resin (B-1) composite spinning are prepared composite fibre, this composite fibre is carried out alkali treatment alkali decomposability resin (B-1) is decomposed the method for removing; After above-mentioned acetal resin (A) and water-soluble resin (B-2) composite spinning prepared composite fibre, this composite fibre is carried out the method that water-soluble resin (B-2) dissolving is removed in water treatment; After above-mentioned acetal resin (A) and organic solvent soluble resin (B-3) composite spinning prepared composite fibre, this composite fibre is carried out organic solvent handle the method that organic solvent soluble resin (B-3) dissolving is removed, can obtain the polyoxymethylene resin fiber of target.
Like this, in a single day the basic principle of the manufacture method of polyoxymethylene resin fiber of the present invention is for after forming composite fibre, compound pairing resin decomposed to remove or dissolve remove, obtain the polyoxymethylene resin fiber of target, its principle and effect and above-mentioned any one method are all equivalent.
Here, as the pairing resin that is used to form composite fibre, so long as have the character of alkali decomposability, water-soluble, organic solvent solubility respectively, then be not particularly limited, can enumerate mylar as alkali decomposability resin (B-1) is typical example, can enumerate polyvinyl alcohol as water-soluble resin (B-2) is typical example, and can enumerate polystyrene as organic solvent soluble resin (B-3) is typical example.
The composite fibre that contains acetal resin (A) and alkali decomposability resin (B-1), water-soluble resin (B-2) or organic solvent soluble resin (B-3) can be by having used the composite spinning preparation of common melt spinning method.For example, use has the device of 2 extruders and composite spinning usefulness mould, to be supplied to the composite spinning mould by acetal resin (A), alkali decomposability resin (B-1), water-soluble resin (B-2) or the organic solvent soluble resin (B-3) of each extruder fusion, extrude by the composite spinning mould, it is reeled, thereby obtain the not composite fibre of stretching.
Then, Yi Bian the composite fibre that stretches continuous or discontinuous heating does not on one side stretch, thus the composite fibre that can obtain to stretch.
Stretch process can be carried out to the temperature range of the fusing point of acetal resin (A) in room temperature, preferably suitably adjusts the stretch process temperature according to draw speed and heating means.
From the uniformity in fiber footpath and the viewpoint of intensity, stretching ratio is preferably more than 3 times, if consider fibre strength and degree of stretching, stretching ratio is preferably more than 4 times, below 15 times.
Composite fibre by stretch processing is according to the characteristic of the compound pairing resin (B-1, B-2, B-3) that uses respectively, carrying out alkali treatment, water treatment or organic solvent handles, compound pairing resin (B-1, B-2, B-3) decomposition or dissolving are removed, thereby can obtain required polyoxymethylene resin fiber.
Treatment conditions are not particularly limited, when mylar that compound pairing resin is the alkali decomposability, use sodium hydrate aqueous solution as treatment fluid, when being water miscible polyvinyl alcohol, compound pairing resin make water as treatment fluid, when polystyrene that compound pairing resin is the organic solvent solubility, use organic solvent such as oxolane as treatment fluid, the method that under any circumstance, can adopt in pressure vessel, handle under the treatment conditions about room temperature～130 ℃.The processing of this composite fibre can be carried out continuous composite fibre, also can to composite fibre is blocked for suitable length, for example the fiber of 1～150mm carries out.
In the manufacture method of the polyoxymethylene resin fiber of the invention described above, the shape of the composite spinning mould that the section shape of gained fiber, fiber footpath etc. can be by changing above-mentioned composite spinning operation is adjusted.In addition, by changing the island structure of the composite fibre that forms by acetal resin (A) and compound pairing resin (B-1, B-2, B-3), also can adjust the section shape of gained polyoxymethylene resin fiber.
For example, as shown in Figure 1 and Figure 2, when in being formed on " sea " of containing compound pairing resin, having the composite fibre on a plurality of " islands " such as the round section that contains acetal resin, triangular cross-section, compound pairing resin is decomposed in post processing or dissolving is removed by it is carried out, and can obtain to have the polyoxymethylene resin fiber of very fine round section, three angle sections etc.The section shape of gained fiber can at random change by the shaped design of composite spinning mould.Like this, be that " sea ", acetal resin are the composite fibre of the island structure on " island " forming with compound pairing resin, in its method of handling, can obtain the polyoxymethylene resin fiber of very fine section.So the fiber that obtains is preferably below the 2dtex, is preferably below the 1dtex especially.
On the other hand, as shown in Figure 3, when in being formed on " sea " of containing acetal resin, having the composite fibre on a plurality of " islands " of containing compound pairing resin, compound pairing resin is decomposed in post processing or dissolving is removed by it is carried out, and can obtain to have the polyoxymethylene resin fiber of complicated special-shaped section.The section shape of gained fiber can at random change by the shaped design of composite spinning mould.
When forming the composite fibre that constitutes as Fig. 4, handle by it being blocked for suitable length utilizes alkali or solvent etc., it can be decomposed or dissolve from truncation surface and remove, the polyoxymethylene resin fiber of the hollow form of compound pairing resin has been removed in acquisition.
As above the polyoxymethylene resin fiber of Huo Deing can use with continuous fibers former state ground, perhaps blocks after suitable fibre length is for example about 1mm～150mm according to application target and uses.
Description of drawings
Fig. 1 is the ideograph of a form of composite spinning mould section shape.
Fig. 2 is the ideograph of other forms of composite spinning mould section shape.
Fig. 3 is the ideograph of another form of composite spinning mould section shape.
Fig. 4 is the ideograph of another form of composite spinning mould section shape.
Need to prove that phase, symbol 2 expressions that 1 expression of symbol among the figure contains acetal resin contain the alkali decomposability beyond the acetal resin or the phase of aqueous solvent dissolubility resin.
Embodiment
Carry out specific description more by the following examples, but the present invention is not limited by it.
The preparation method of＜polyacetal copolymer 〉
The basic preparation method of the polyacetal copolymer that uses in embodiment and comparative example is as follows.
Use has the cylinder of partly overlapping section shape and has the continous mode hybrid reaction machine that rotating shaft constituted of blade by being with in the outside by the sleeve pipe of heat (cold) medium, 2 circles, 2 rotating shafts that have blade are rotated on one side respectively with 150rpm, add aqueous three alkane and comonomer on one side, and then will be as the dimethoxym ethane of molecular weight regulator, the catalyst boron trifluoride (with respect to total monomer) with 50pmm supplies in the polymerization machine continuously simultaneously, carries out block polymerization simultaneously.
The product of discharging from the polymerization machine is promptly led to disintegrating machine, joins simultaneously in 60 ℃ of aqueous solution that contain 0.05 weight % triethylamine, makes catalysqt deactivation, so separate, washing, drying, obtain thick polyacetal copolymer.
Then, this thick polyacetal copolymer with respect to 100 weight portions, add 4 weight portions the triethylamine 5 weight % aqueous solution, [3-(3 for the pentaerythrite four of 0.3 weight portion, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], use 2 screw extruders at 210 ℃ of following melting mixings, remove l fraction.
Then, [3-(3 to add pentaerythrite four as 0.03 weight portion of stabilizing agent in the polyacetal copolymer of 100 weight portions, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] and the melamine of 0.15 weight portion, use 2 screw extruders at 210 ℃ of following melting mixings, obtain stable graininess polyacetal copolymer.
Use the preparation method of above-mentioned polyacetal copolymer, and the polyacetal copolymer that preparation is used in an embodiment (polyacetal copolymer that uses in POM-1～POM-6), the comparative example (POM-7～POM-10).
Need to prove, in POM-5, use the diethylene glycol formal, in POM-6, use 1,4-butanediol formal, in addition use 1, the 3-dioxolanes as comonomer.In addition, adjust by the amount of employed comonomer in the copolymerization with respect to the ratio of the oxyalkylene units (copolymerization units) of 100mol formaldehyde unit, melt index (MI) (MI) is adjusted by the increase and decrease as the dimethoxym ethane amount of molecular weight regulator.Melt index (MI) (MI) can increase by the amount that increases dimethoxym ethane, reduces by the amount that reduces dimethoxym ethane.
The melt index (MI) of prepared polyacetal copolymer (MI) is according to ASTMD-1238, measures under 190 ℃, the loading of 2160g.In addition, polymer composition (ratio of copolymerization units) is following quantitatively: each polyacetal copolymer is dissolved among the hexafluoroisopropanol d2 carries out
1H-NMR measures, and is undertaken quantitatively by the peak area corresponding to each unit.
Use above-mentioned preparation copolyoxymethylenes (POM-1～POM-6 and POM-7～POM-10), as follows, at first prepare composite fibre, then compound pairing material is decomposed and removes or dissolve, thereby the preparation polyoxymethylene resin fiber.
At first, when the preparation composite fibre, use mylar (polybutylene terephthalate (PBT)) as compound pairing material.
Composite spinning uses to have 2 extruders and composite spinning and carries out with the device of mould, utilize an extruder (200 ℃ of cylinder design temperatures) with above-mentioned copolyoxymethylenes fusion plasticising, utilize another extruder (270 ℃ of cylinder design temperatures) with above-mentioned polyester (polybutylene terephthalate (PBT)) fusion plasticising, utilize each gear pump to measure two compositions of plasticising, be conducted in the composite spinning mould with section shape shown in Figure 1, by its nozzle spinning, after the taking-up, obtain to contain the not stretching composite fibre of copolyoxymethylenes and mylar (polybutylene terephthalate (PBT)).Then, utilize the hot-blast heater that is set at 138 ℃ to heat this composite fibre that do not stretch, be stretched to 7 times simultaneously, thereby obtain the composite fibre of the stretching of 2.5dtex.
Then, the composite fibre that as above obtains is dropped in 10% sodium hydrate aqueous solution, in pressure vessel, be heated to 130 ℃, thereby decomposing, removes in the mylar (polybutylene terephthalate (PBT)) that will constitute composite fibre " sea ", and then carry out water washing, drying, thereby obtain to contain the superfine fibre of acetal resin.
Evaluation is that the fiber process of the preparatory phase of preparation, particularly composite fibre according to above-mentioned polyoxymethylene resin fiber is carried out.The results are shown in the table 1.
Table 1
Combined polymerization unit ratio: expression is with respect to the ratio (mol) of 100mol formaldehyde unit.
Claims (8)
1. the manufacture method of polyoxymethylene resin fiber, it is characterized in that, every 100mol formaldehyde repetitive is contained oxyalkylene units shown in the following general formula (1) of 1.5～8.0mol, at 190 ℃, the melt index (MI) that the loading of 2160g is measured down is 1～120g/10 minute acetal resin (A) and is selected from alkali decomposability resin (B-1), after thermoplastic resin (B) composite spinning of water-soluble resin (B-2) and organic solvent soluble resin (B-3) prepares composite fibre, this composite fibre is carried out alkali treatment, water treatment or organic solvent are handled, thermoplastic resin (B) decomposed to remove or to dissolve remove
In the formula, R
1, R
2Be selected from the alkyl of hydrogen, carbon number 1～8, the organic group with alkyl of carbon number 1～8, phenyl, have the organic group of phenyl, R
1, R
2Can be the same or different; M represents 2～6 integer.
2. the manufacture method of the polyoxymethylene resin fiber of claim 1, wherein alkali decomposability resin (B-1) is a mylar.
3. the manufacture method of the polyoxymethylene resin fiber of claim 1, wherein water-soluble resin (B-2) is a polyvinyl alcohol.
4. the manufacture method of the polyoxymethylene resin fiber of claim 1, wherein organic solvent soluble resin (B-3) is a polystyrene.
5. the manufacture method of each described polyoxymethylene resin fiber of claim 1～4, wherein acetal resin (A) is for containing the polyacetal copolymer of oxyalkylene units shown in the described general formula of 1.8～5.0mol (1) with respect to 100mol formaldehyde repetitive.
6. the manufacture method of each described polyoxymethylene resin fiber of claim 1～4, wherein acetal resin (A) is for containing the polyacetal copolymer of oxyalkylene units shown in the described general formula of 2.0～4.0mol (1) with respect to 100mol formaldehyde repetitive.
7. the manufacture method of each described polyoxymethylene resin fiber of claim 1～4, wherein the section shape of polyoxymethylene resin fiber is circular, polygon or hollow.
8. the manufacture method of each described polyoxymethylene resin fiber of claim 1～4, wherein the fiber number of polyoxymethylene resin fiber is below the 2dtex.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006179948A JP4912768B2 (en) | 2006-06-29 | 2006-06-29 | Method for producing polyoxymethylene resin fiber |
| JP2006-179948 | 2006-06-29 | ||
| JP2006179948 | 2006-06-29 |
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|---|---|
| CN101096784A CN101096784A (en) | 2008-01-02 |
| CN101096784B true CN101096784B (en) | 2011-11-23 |
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|---|---|
| JP (1) | JP4912768B2 (en) |
| KR (1) | KR101345032B1 (en) |
| CN (1) | CN101096784B (en) |
| WO (1) | WO2008001924A1 (en) |
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| JP5168467B2 (en) * | 2007-03-20 | 2013-03-21 | Ｅｓファイバービジョンズ株式会社 | Split type composite fiber containing polyacetal, and fiber molded body and product using the same |
| CN102011201B (en) * | 2010-12-15 | 2012-10-10 | 四川省纺织科学研究院 | Melt-spinning method for polyformaldehyde fibers |
| CN107407010B (en) * | 2015-03-18 | 2020-10-20 | 三菱瓦斯化学株式会社 | Antibacterial fiber |
| CN110892100B (en) * | 2017-07-14 | 2022-05-13 | 三菱瓦斯化学株式会社 | Method for producing polyacetal fiber |
| EP3653767A4 (en) * | 2017-07-14 | 2020-07-29 | Mitsubishi Gas Chemical Company, Inc. | Method for producing polyacetal fiber |
| CN107586373A (en) * | 2017-10-18 | 2018-01-16 | 江苏苏博特新材料股份有限公司 | A kind of crystal property adjustable spinning polyoxymethylene resin and its spinning process |
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| CN1572920A (en) * | 2003-06-09 | 2005-02-02 | 汎塑料株式会社 | Nonwoven fabric made from polyformaldehyde resin and its making method |
| CN1667165A (en) * | 2004-03-09 | 2005-09-14 | 汎塑料株式会社 | Polyformaldehyde resin made twisting yarn |
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| JPS6253413A (en) * | 1985-08-31 | 1987-03-09 | Asahi Chem Ind Co Ltd | Fiber structure having excellent weather resistance |
| JPH1037065A (en) * | 1996-07-24 | 1998-02-10 | Toray Ind Inc | See-through proofing fiber and its production |
| JPH11293523A (en) * | 1998-04-15 | 1999-10-26 | Unitika Ltd | Polyoxymethylene filament having high specific gravity |
| JP4907023B2 (en) * | 2001-09-18 | 2012-03-28 | ポリプラスチックス株式会社 | Method for producing polyoxymethylene fiber |
| JP4260392B2 (en) * | 2001-12-14 | 2009-04-30 | ポリプラスチックス株式会社 | Flat yarn made of polyoxymethylene resin, its production method and use |
| JP2005105452A (en) * | 2003-09-30 | 2005-04-21 | Gun Ei Chem Ind Co Ltd | Conjugate fiber, phenol resin-based ultrafine fiber, phenol resin-based ultrafine carbon fiber, phenol resin-based ultrafine active carbon fiber and method for producing them |
| JP4350625B2 (en) * | 2003-10-09 | 2009-10-21 | 株式会社クラレ | Ultra-thin fiber nonwoven fabric, production method thereof and use thereof |
| JP4874530B2 (en) * | 2004-06-25 | 2012-02-15 | ポリプラスチックス株式会社 | Polyoxymethylene resin fiber and method for producing the same |
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- 2007-06-26 WO PCT/JP2007/063198 patent/WO2008001924A1/en active Application Filing
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1572920A (en) * | 2003-06-09 | 2005-02-02 | 汎塑料株式会社 | Nonwoven fabric made from polyformaldehyde resin and its making method |
| CN1667165A (en) * | 2004-03-09 | 2005-09-14 | 汎塑料株式会社 | Polyformaldehyde resin made twisting yarn |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080002647A (en) | 2008-01-04 |
| CN101096784A (en) | 2008-01-02 |
| WO2008001924A1 (en) | 2008-01-03 |
| JP2008007892A (en) | 2008-01-17 |
| KR101345032B1 (en) | 2013-12-26 |
| JP4912768B2 (en) | 2012-04-11 |
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