EP4202093A1 - Multifilament de polyamide et procédé de fabrication de celui-ci - Google Patents
Multifilament de polyamide et procédé de fabrication de celui-ci Download PDFInfo
- Publication number
- EP4202093A1 EP4202093A1 EP21858180.9A EP21858180A EP4202093A1 EP 4202093 A1 EP4202093 A1 EP 4202093A1 EP 21858180 A EP21858180 A EP 21858180A EP 4202093 A1 EP4202093 A1 EP 4202093A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyamide
- dtex
- multifilament
- tenacity
- polyamide multifilament
- 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.)
- Pending
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 122
- 229920002647 polyamide Polymers 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 239000000470 constituent Substances 0.000 claims description 4
- 238000010036 direct spinning Methods 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 30
- 239000000835 fiber Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- 239000012770 industrial material Substances 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 11
- 239000004753 textile Substances 0.000 description 11
- 229920002302 Nylon 6,6 Polymers 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 238000009987 spinning Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 230000003247 decreasing effect Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000002040 relaxant effect Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002729 catgut Substances 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920006118 nylon 56 Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
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
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
- D01D5/092—Cooling filaments, threads or the like, leaving the spinnerettes in shafts or chimneys
-
- 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
- D01D5/08—Melt spinning methods
- D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/063—Load-responsive characteristics high strength
Definitions
- the present invention relates to a polyamide multifilament.
- a multifilament of polyamide 6 also known as “polycaprolactam” or polyamide 66 (also known as “polyhexamethylene adipamide”) has higher tenacity and elongation and better fluffy quality than a general-purpose multifilament of polyester, polypropylene, or the like, and thus, is used in various industrial applications such as air bags, catgut for sports rackets, ropes, fishing nets, and belts for bags.
- Air bags which have been rapidly increasing in the ratio of installation as essential safety devices for protecting passengers in a collision between vehicles, are continuing to increase in terms of the points of installation, for example, an air bag for protection of the knee, an air bag built in a sheet for a seat to protect the chest, and an air bag built in the ceiling above the window to protect the head, in addition to air bags that have been installed for protection of a driver and a front passenger since the initial days.
- An increase in the number of the points of installation, a demand for lower fuel consumption to be improved year after year, and a recent years' tendency to expand the space in a vehicle are accompanied by various studies to develop a lighter and more compact base cloth to be used for an air bag.
- the total fineness of a polyamide 66 yarn to be used for an air bag base cloth was generally 940 dtex in the past, but in recent years, a 470 dtex yarn has been used mainly, and furthermore, a yarn having a fineness as low as 235 dtex or less is also used.
- Patent Literature 1 and Patent Literature 2 disclose a technology that affords a polyamide fiber that has a low fineness and a high tenacity with high fluffy quality and can provide an air bag having excellent compactness.
- the total fineness proposed is 100 to 250 dtex in Patent Literature 1 and 50 to 470 dtex in Patent Literature 2.
- the section does not describe any specific example of a yarn the total fineness of which is made as low as 150 dtex or less, furthermore 100 dtex or less, and which has a high tenacity and thus can be used as an industrial fiber.
- the reason for this is, as described in Patent Literature 1 (paragraph [0021]), that a lower total fineness makes it more difficult to stably obtain a fiber having a high tenacity.
- obtaining a multifilament having a low total fineness involves increasing the influence of the retention of the molten state of polyamide chips melted before being spun and the influence of defects such as voids remaining in the fiber being spun. That is, no consideration is taken of a problem that will be caused when a multifilament having a fineness of 100 dtex or less is produced using an apparatus such as a direct drawing machine that is included in common facilities for producing fibers for industrial materials having a high tenacity, such as a yarn for air bags, and that is a combination of a spinning unit for a high total fineness of approximately 235 to 2000 dtex and a multistage heat-drawing machine for developing a high tenacity.
- Patent Literature 5 discloses a means by which yarn is drawn and heat-fixed, or heat-drawn, once wound on a package, further brought in contact with a hot plate heated to 170 to 205°C, and thereby heat-drawn 1.15-fold or more.
- this means involves a method including two separated processes, i.e. a spinning process and a drawing process.
- a spinning process i.e. a spinning process
- a drawing process i.e. a spinning process and a drawing process.
- Patent Literature 6 a product obtained by a step that could be commercialized was only a polyamide multifilament having a tenacity up to 7.3 cN/dtex at best, and the tenacity was insufficient for an attempt to enhance the durability of fibers for industrial materials such as air bags and that of textiles for clothing.
- An object of the present invention is to solve the above-mentioned problems, to provide a polyamide multifilament having a low fineness, a high tenacity, excellent toughness, and in addition, good fluffy quality, and to provide a polyamide multifilament that makes it possible to attempt to decrease the weight of an industrial material such as an air bag, and to enhance the durability of a textile for clothing, as above-mentioned.
- the present invention makes it possible to obtain a polyamide multifilament which is good also in terms of production efficiency.
- the present invention has been made through a vigorous study to solve the above-mentioned problems, and is mainly composed of the following constituents.
- the present invention can provide a polyamide multifilament having a low fineness and nonetheless having a high tenacity, excellent toughness, and in addition, good fluffy quality, and makes it possible to attempt to decrease a weight of an industrial material, and to enhance durability of a textile for clothing.
- Fig. 1 is a schematic diagram for describing an example of a step of producing a polyamide multifilament according to the present invention.
- Examples of a raw material to be used for a polyamide multifilament according to the present invention include: nylon 6; nylon 66; nylon 12; nylon 46; nylon 56; nylon 610; copolymer polyamides of nylon 6 and nylon 66; copolymer polyamides obtained by copolymerizing nylon 6 with a polyalkylene glycol, dicarboxylic acid, diamine or other copolymerizable monomers. These are known as polymers containing repeating units linked via an amide bond. Such a material is subject to no particular limitation as long as the material is a polyamide. Among these materials, polyamide 66 having excellent impact resistance and heat resistance is preferably used.
- a polyamide multifilament according to the present invention may contain a component other than a polyamide.
- a component include: end-capping agents such as monocarboxylic acids; delustering agents such as titanium oxide; polymerization catalysts and heat resistance promoters, such as phosphorus compounds; and antioxidants and heat stabilizers, such as copper compounds and halides of alkali metals or alkaline earth metals.
- the content ratio of the polyamide in the polyamide multifilament is preferably 95 wt% or more, more preferably 97 wt% or more. In cases where the content ratio of the polyamide is less than 95 wt%, the heat resistance is decreased in some cases.
- a polyamide multifilament according to the present invention has a total fineness of 30 to 150 dtex.
- the total fineness is more preferably in the range of from 50 to 120 dtex. With the total fineness of less than 30 dtex, it is difficult to achieve a sufficient value as the total strength of the multifilament, and, in addition, drawing at a high ratio to obtain a high tenacity tends to cause single yarn breakage, and also has a higher possibility of generating fluffs.
- the total fineness of more than 150 dtex does not lead to decreasing the weight of an industrial material or to enhancing the durability of a textile for clothing.
- the tenacity of a polyamide multifilament according to the present invention is 7.5 to 10.0 cN/dtex, more preferably 8.0 to 9.7 cN/dtex. Having a tenacity in such a range allows the polyamide fiber to be suitable for industrial materials such as air bags and for textiles for clothing that have excellent durability.
- the tenacity of less than 7.5 cN/dtex is insufficient to enhance the durability of fibers for industrial materials such as air bags and that of textiles for clothing.
- Bringing the tenacity of the polyamide fiber to more than 10.0 cN/dtex involves mechanical drawing at a high ratio, tends to generate single yarn breakage, and in addition, degrades fluffy quality.
- Such a polyamide multifilament is unsuitable for quality-demanding fibers for industrial materials such as air bags.
- a polyamide multifilament according to the present invention has an elongation at break of 15.0% to 35.0%, more preferably 17.0% to 30.0%. The higher the elongation at break, the more preferable. The elongation at break is realistically 35.0% or less to obtain a predetermined tenacity with a polyamide. This range makes it possible to increase the toughness of the polyamide multifilament and the amount of work to break, and to maintain excellent durability.
- the product of a tenacity and a square root of elongation is preferably 38 cN/dtex. (% 1/2 ) or more, more preferably 40 cN/dtex ⁇ (% 1/2 ) or more. Having a high product of a tenacity and a square root of elongation makes it possible to inhibit generation of fluffs, yarn breakage, and the like, and thus, to obtain a polyamide multifilament having a high tenacity and nonetheless having extremely high quality.
- the tenacity (cN/dtex) and the elongation at break (%) each refer to a value measured under the conditions of constant rate of elongation that are described in JIS L1013 (1999), 8.5.1 Standard-condition Test.
- the product of a tenacity and a square root of elongation is a value calculated in accordance with [tenacity ⁇ ⁇ (elongation at break)].
- the upper limit is subject to no particular limitation, and is practically 50.0 cN/dtex. (% 1/2 ) or less.
- a polyamide multifilament according to the present invention preferably has an uster unevenness (U%) of 1.2% or less.
- the user unevenness is still more preferably 1.0% or less, particularly preferably 0.8% or less. Bringing the U% to 1.2% or less allows a textile for clothing to generate no uneven dyeing or no streak during dyeing, and to have good appearance and excellent product quality.
- the lower limit is subject to no particular limitation, and is practically 0.3% or more.
- a polyamide multifilament according to the present invention preferably has a variation coefficient of elongation of 1.00% or less at 3 cN/dtex.
- the variation coefficient of elongation at 3 cN/dtexs is still more preferably 0.80% or less, particularly preferably 0.50% or less.
- Having the variation coefficient of 1.00% or less makes it possible that, when a given load is applied to an industrial textile such as an air bag, the elongation at break of the multifilament is uniformized.
- the variation coefficient is due to the irregularity of the crystal structure, and thus, is related to inhibiting uneven dyeing in the case of a textile for clothing.
- a simple means of decreasing the variation coefficient of elongation at 3 cN/dtex to 1.00% or less is to control a difference between sulfuric acid relative viscosity of polyamide chips to be used and sulfuric acid relative viscosity of the resulting polyamide multifilament.
- this difference in viscosity is large, the raw material chips before being made into yarns undergo local viscosity increase or hydrolysis due to thermal cross-linking or the like.
- Such viscosity increase generates spots at which the crystalline orientation is locally increased in the longitudinal direction of the fibers, and such hydrolysis generates spots at which the crystalline orientation is locally decreased in the longitudinal direction of the fibers.
- the elongation at break is prone to undergo irregularity.
- the variation coefficient of elongation at 3 cN/dtex is determined by the method described in the Examples section.
- a polyamide multifilament according to the present invention preferably has 0 to 3 fluffs/10,000 m or less, particularly 0 to 2 fluffs/10,000 m, more preferably 0 to 1 fluff/10,000 m. Having a smaller number of fluffs makes it possible to expand the uses to articles desired to have excellent fluffy quality, such as air bags.
- the number of fluffs refers to a value converted to the number of fluffs/10,000 m from the total number of fluffs measured along a filament having a length of 100,000 m or more while the filament is rewound at a rate of 150 m/minute.
- the number of voids contained in the polyamide filament as a constituent of the polyamide multifilament is preferably 50 voids/cm or less, that is, 0 to 50 voids/cm, particularly 0 to 30 voids/cm, more preferably 0.2 to 20 voids/cm.
- the number of voids contained in the polyamide filament is more than 50 voids/cm, the tenacity of the single filament containing the voids is decreased. This means that the voids in the single filament inhibit drawing.
- the polymer being melted excessively takes in moisture from the air, and thereby causes hydrolysis, causes a decrease in the viscosity of the polyamide, and leaves the crystalline orientation insufficient, resulting in a decrease in the tenacity.
- the fluffy quality is degraded.
- a method of decreasing the voids include a method in which the pressure at which polyamide is extruded by an extruder is adjusted to 20.0 to 80.0 kPa.
- Fig. 1 is a schematic diagram of a direct spinning and drawing machine to be preferably used in the present invention.
- raw material chips of polyamide are provided as a raw material for a polyamide multifilament according to the present invention.
- a method of polymerizing a polyamide any known polymerization method can be used.
- Sulfuric acid relative viscosity of the polyamide raw material chips to be used for a polyamide multifilament according to the present invention is preferably 2.8 to 3.9, more preferably 3.3 to 3.9.
- viscosity is preferably 2.8 to 3.9, more preferably 3.3 to 3.9.
- the chips having a viscosity of 4.0 or more With the chips having a viscosity of 4.0 or more, bringing the total fineness into a range prescribed in the present invention leads to generating minute foreign matter due to viscosity increase, thermal degradation, and gelation caused by the long-time retention of the polymer, and thus, degrading the fluffy quality.
- the chips having a viscosity of less than 2.8 it is difficult to obtain a polyamide multifilament having a tenacity prescribed in the present invention.
- the sulfuric acid relative viscosity refers to a value obtained by using an Ostwald viscometer at 25°C to measure the viscosities of the following: a solution of 1 g of chips dissolved in 100 ml of 98% sulfuric acid; and 98% sulfuric acid having no chip dissolved therein. The details of the measurement are as described in the Examples section.
- a method of direct spinning and drawing is used, and that
- is less than 0.2.
- ⁇ 0.3 has extremely good fluffy quality and high tenacity and elongation, and can be obtained as a polyamide multifilament having less irregularity in the elongation at break when elongated 3%.
- ⁇ 0.3 inhibits viscosity increase and thermal degradation due to the long-time retention of the polymer, or inhibits the hydrolysis of the polyamide.
- the polyamide multifilament produced can be sorted out in an inspection step after the production, if such sorting-out is permissible from a productivity point of view.
- the pressure at the feeding unit in the extruder is preferably not a vacuum (having a pressure of 0.0 kPa) but 20.0 to 80.0 kPa in order to inhibit the viscosity increase, thermal degradation, and gelation of the polymer.
- the pressure is more preferably 40.0 to 60.0 kPa.
- the fluffy quality is degraded owing to the viscosity increase, thermal degradation, and gelation of the polymer, and in addition, yarn having a high tenacity cannot be obtained.
- the pressure at the feeding unit in the extruder is 80.0 kPa or more, the number of voids contained in the polyamide filament is increased, and furthermore, the hydrolysis reaction of the polymer is predominant, thus making it not possible to obtain a yarn having a high tenacity.
- polyamide spun through a spinneret 1 is preferably allowed to pass through a heating hood 2 surrounding the range 5 to 300 cm immediately below the spinneret.
- the temperature in this heating hood is -30 to +30°C, more preferably -15 to +15°C, with respect to the melting point of the polymer polyamide.
- the yarn spun out is not immediately cooled but slowly cooled through the high-temperature atmosphere surrounded by the above-mentioned heating hood. Thereby, the orientation of the polyamide molecules melt-spun is relaxed, and makes it possible to enhance the molecular orientation uniformity between single filaments, thus enabling the polyamide multifilament to have a higher tenacity.
- An undrawn yarn 5 that has passed through the high-temperature atmosphere is then blown by air at 10 to 80°C, preferably 10 to 50°C, using a cross flow cooling device 3, and thus cooled and solidified. Additionally, in cases where the cooling air is more than 80°C, the single filaments are more shaken during spinning, and thus, for example, the single filaments collide thereamong, resulting in difficulty in yarn production.
- the cooled yarn is provided with an oil agent using a known oil supply device 4, taken up on a take-up roll 6, drawn, and then can be wound up.
- an oil agent any known oil can be used.
- the amount of application is preferably 0.3 to 1.5 wt%, still more preferably 0.5 to 1.0 wt%, to inhibit the entwinement of the single yarns around the take-up roll 6.
- the spinning rate defined by the rotational speed of the take-up roll 6 is preferably 500 to 1200 m/minute, more preferably 600 to 800 m/minute. With the spinning rate at 500 m/minute or more, the final production speed is sufficient, and the polyamide multifilament can be produced inexpensively with high production efficiency.
- the spinning rate of 1200 m/minute or less makes it possible to inhibit a generation of fluff and yarn breakage, and thus, is preferable.
- the drawing rate represented by the maximum speed of the drawing roll is preferably 2800 m/minute or more, more preferably 3000 m/minute or more.
- Such an undrawn yarn obtained by the above-mentioned method can be drawn, undergo relaxation heat treatment, be wound up, and so on using a known method.
- the undrawn yarn taken up on the take-up roller 6 (1FR) is wound up on a feeding roller 7 (2FR), a first drawing roller 8 (1DR), a second drawing roller 9 (2DR), and a relaxing roller 10 (RR) in this order, heat-treated and drawn, and wound up on a winder 11.
- a prestretch drawing is performed between 1FR and 2FR, a 1st-stage drawing is performed between 2FR and 1DR, and a 2nd-stage drawing is performed between 1DR and 2DR.
- the temperature for 2FR is set at 30 to 50°C
- the temperature for 1DR is set at 100 to 225°C
- the prestretch drawing and the 1st-stage drawing are heat-drawing processes performed at and around the glass transition temperature.
- the remaining drawing and heat-setting processes are usually preferably performed in the temperature range of from 180 to 240°C.
- the temperature is more preferably 200 to 220 °C.
- a total draw ratio (hereinafter referred to simply as a "draw ratio"), that is, a ratio at which drawing is performed between the take-up roller 6 and the second drawing roller 9, a high draw ratio is preferably adopted to afford a polyamide multifilament having a high tenacity, and the draw ratio has only to be 3.8 to 5.0 as long as the ratio allows the fineness to fall within the range described in the present invention.
- the winding speed is usually preferably 2000 to 5000 m/minute, more preferably 2500 to 4500 m/minute.
- the yarn is preferably wound up in the form of a cheese stripe using a winding device under conditions where the winding tension is 20 to 250 gf.
- Using the method described above makes it possible to inhibit the viscosity increase, thermal degradation, gelation, and hydrolysis of the polyamide polymer, lessen the influence of the voids on the mechanical properties, and obtain a polyamide multifilament having a low fineness of 150 dtex or less as a total fineness, and nonetheless having a high tenacity and high elongation at break, that is, high toughness, and in addition, good quality.
- An aqueous solution of 5 wt% copper acetate as an antioxidant was added to and mixed with nylon 66 chips obtained by liquid-phase polymerization, so that copper was added and adsorbed at 68 ppm with respect to the weight of the polymer.
- an aqueous solution of 50 wt% potassium iodide and an aqueous solution of 20 wt% potassium bromide were added to and adsorbed in the polymer chips in such a manner that the ratio of the potassium from each solution was 0.1 part by weight with respect to 100 parts by weight of the polymer chips.
- the resulting mixture was solid-phase-polymerized using a batch type solid-phase polymerization device to obtain nylon 66 pellets having a sulfuric acid relative viscosity of 3.75.
- the resulting nylon 66 pellets were supplied into an extruder having a diameter of 110 mm, and melted in an atmosphere where the melting temperature was 300°C, and where the pressure at the feeding unit in the extruder was 50.0 kPa.
- the amount of the molten polymer was adjusted with a measuring pump so as to afford a multifilament having a total fineness of 80 dtex, and the molten polymer was fed into a spinning pack.
- the molten polymer was filtrated through a metal nonwoven filter having a coarseness of 40 ⁇ m in the spinning pack, allowed to pass through a spinneret having 24 circular holes, and spun using an apparatus configured as depicted in Fig. 1 .
- a heating hood having a length of 20 cm was disposed 3 cm below the spinneret face, and heated in such a manner that the atmospheric temperature in the hood was 250°C.
- the atmospheric temperature in the hood is the temperature of the air in the portion that is in the center of the heating hood in the length direction and is 1 cm apart from the inner wall.
- a cross flow type chimney for blowing air unidirectionally was attached, and the yarn was blown by cold air at 18°C at a rate of 35 m/minute to be cooled and solidified. Then, the yarn was provided with an oil.
- the undrawn yarn provided with the oil was wound and taken up on the 1FR rotating at a surface speed of 800 m/minute, and then drawn at a total draw ratio of 4.3. Without being once wound up, the yarn taken up was continuously stretched 5% between the take-up roller and the 2FR, subsequently drawn at a rotational speed ratio of 2.80 in the 1st stage, then drawn at a rotational speed ratio of 1.46 in the 2nd-stage, and wound up at a rate of 3400 m/minute.
- the surface of each of the 1FR and 2FR rollers was mirror-finished, and that of each of the 1DR, 2DR, and RR was satin-finished.
- each roller was set as follows: 1FR, non-heated; 2FR, 40°C; 1DR, 150°C; 2DR, 225°C; and RR, 150°C.
- melt-spinning and drawing afforded a nylon 66 multifilament.
- high-pressure air was sprayed perpendicularly onto the yarn running through an entangling device.
- a guide for regulating the running yarn was provided before and after the entangling device.
- the pressure of the air to be sprayed was set constantly at 0.2 MPa.
- Example 1 The results obtained by evaluating the properties of these polyamide multifilaments obtained in Examples 1 to 12 are tabulated in Table 1.
- Table 1 Item Example 1
- Example 2 Example 3
- Example 4 Example 5
- Example 6 Example 7
- Example 8 Example 9
- Example 10 Example 11
- Example 12 Total fineness (dtex) 80 50 110 30 135
- Number of filaments 24 24 24 24 72 10 136 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 Single-filament fineness (dtex) 3.3 2.1 4.6 1.3 5.6 1.1 8.0 0.6 3.3 3.3 3.3 3.3 3.3
- Pressure at feeding unit in extruder (kPa) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 25.0 75.0 Total draw ratio 4.3 4.3 4.3 4.1 4.3 4.3 4.3 4.3 3.6 3.9
- 4.0 Winding speed (m/min) 3600 3600 3600 3600 3600 3600
- the polyamide multifilament according to the present invention has a low fineness and a high tenacity, and nonetheless has good fluffy quality.
- Example 1 to 5 different polyamide multifilaments according to the present invention that have different total finenesses were produced. Compared with Examples 11 and 12 and the below-mentioned Comparative Examples 1 to 5, melting the polymer in an atmosphere having a pressure of 50.0 kPa at the feeding unit in the extruder made it possible to inhibit viscosity increase, and to obtain a polyamide multifilament of interest. In addition, as the total fineness was decreased, and as the single-filament fineness was lowered, cooling was more advantageous, and thus, the product of a tenacity and a square root of elongation of the polyamide multifilament tended to be increased.
- Example 11 to 12 are examples in which yarn was made with the pressure set at 25.0 kPa and 75.0 kPa respectively at the feeding unit in the extruder. Viscosity increase or hydrolysis tended to occur in the process from the chips to the multifilament, and influence on the variation coefficient of elongation at 3 cN/dtex was observed.
- This Reference Example was performed in the same manner as in Example 1 except that the total fineness of the polyamide multifilament was changed to 175 dtex, and that the pellets were melted in an atmosphere having a pressure of 0.0 kPa at the feeding unit in the extruder.
- Comparative Example 1 a polyamide multifilament having a total fineness of 110 dtex was produced in the same manner as in Reference Example 1, but in this case, it was not possible to make yarn.
- Comparative Example 2 a polyamide multifilament was made into yarn in the same manner as in Comparative Example 1 except that the draw ratio was 3.6. It was possible to make yarn.
- the resulting polyamide multifilament underwent viscosity increase and thermal degradation due to the long-time retention of the polymer, lost tenacity, and generated many fluffs.
- Comparative Example 3 a polyamide multifilament having a total fineness of 80 dtex was produced under the same yarn-making conditions as in Comparative Example 2, but in this case, it was not possible to make yarn.
- Comparative Example 4 a polyamide multifilament was made into yarn in the same manner as in Comparative Example 3 except that the draw ratio was decreased to 3.2. It was possible to make yarn.
- the resulting polyamide multifilament underwent viscosity increase and degradation due to the long-time retention of the polymer, lost tenacity, and generated many fluffs.
- Example 5 a multifilament was produced in the same manner as in Example 1 except that the polymer was melted in an atmosphere having a pressure of 101.3 kPa at the feeding unit in the extruder, but in this case, the hydrolysis reaction of the polymer was markedly significant, with the result that the viscosity of the multifilament was much below the viscosity of the chips. Furthermore, an increase in the amount of voids in the yarn caused many fluffs to be generated, thus making it not possible to achieve a tenacity prescribed in the present invention.
- Reference Example 2 is an example in which a polyamide multifilament was produced in accordance with WO2016/076184 in common facilities for producing fibers for clothing.
- the retention time of the polymer was short, and thus the polymer was hardly increased in viscosity.
- the number of drawing stages was one, and in addition, the draw ratio was low.
- the tenacity was not sufficient, and in addition, the crystal structure tended to cause irregularity in the longitudinal direction of the fiber, exhibiting a large influence on the variation coefficient of elongation at 3 cN/dtex.
- a polyamide multifilament according to the present invention has a low fineness and a high tenacity and good fluffy quality, and thus, is suitable mainly in attempts to decrease the weight of an industrial material such as an air bag, and to enhance the durability of a textile for clothing.
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- Engineering & Computer Science (AREA)
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- Chemical & Material Sciences (AREA)
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JP2020139838 | 2020-08-21 | ||
PCT/JP2021/029073 WO2022039033A1 (fr) | 2020-08-21 | 2021-08-05 | Multifilament de polyamide et procédé de fabrication de celui-ci |
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EP4202093A1 true EP4202093A1 (fr) | 2023-06-28 |
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EP21858180.9A Pending EP4202093A1 (fr) | 2020-08-21 | 2021-08-05 | Multifilament de polyamide et procédé de fabrication de celui-ci |
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US (1) | US20230279586A1 (fr) |
EP (1) | EP4202093A1 (fr) |
JP (1) | JPWO2022039033A1 (fr) |
CN (1) | CN115803484A (fr) |
TW (1) | TW202219342A (fr) |
WO (1) | WO2022039033A1 (fr) |
Family Cites Families (25)
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FR1481544A (fr) * | 1965-05-29 | 1967-05-19 | Asahi Chemical Ind | Articles filamenteux en polyamide possédant une section transversale cellulaire, etprocédé pour leur production |
JPS4846696A (fr) * | 1971-10-14 | 1973-07-03 | ||
JPH05171512A (ja) * | 1991-12-26 | 1993-07-09 | Toray Ind Inc | 透明性に優れた高強度ポリアミドモノフィラメントの製造方法 |
US5344708A (en) * | 1992-05-12 | 1994-09-06 | E. I. Du Pont De Nemours And Company | Bulked random copolyamide yarns of nylon 6 and nylon 6,6 having enhanced dyeability |
JP3121149B2 (ja) * | 1992-06-18 | 2000-12-25 | 旭化成工業株式会社 | インクリボン用繊維 |
JP3121968B2 (ja) * | 1993-10-22 | 2001-01-09 | 帝人株式会社 | ポリアミドモノフィラメントおよびその製造方法 |
JPH08296116A (ja) * | 1995-04-28 | 1996-11-12 | Teijin Ltd | 全芳香族ポリアミド繊維の製造法 |
JPH11129846A (ja) * | 1997-10-28 | 1999-05-18 | Toray Ind Inc | エアバッグ用基布およびその製造方法 |
JPH11247022A (ja) | 1998-02-27 | 1999-09-14 | Scalar High Touch Kk | 細繊度超高強度ナイロン糸の製造方法および細繊度超高強度ナイロン糸 |
JP2002088577A (ja) | 2000-09-13 | 2002-03-27 | Toray Ind Inc | ポリアミド繊維およびその製造方法ならびにその用途 |
JP4733299B2 (ja) | 2001-07-05 | 2011-07-27 | 旭化成せんい株式会社 | ポリアミド繊維 |
US6899836B2 (en) * | 2002-05-24 | 2005-05-31 | Invista North America S.A R.L. | Process of making polyamide filaments |
JP5087949B2 (ja) | 2006-02-27 | 2012-12-05 | 東レ株式会社 | ポリアミド繊維 |
JP2008133566A (ja) | 2006-11-29 | 2008-06-12 | Toray Ind Inc | ポリアミド繊維の製造方法 |
JP4992577B2 (ja) * | 2007-06-29 | 2012-08-08 | 東レ株式会社 | ポリアミドマルチフィラメントおよびそれを用いた織物 |
JP2009242963A (ja) * | 2008-03-28 | 2009-10-22 | Toray Ind Inc | ポリカプラミド系製糸材料 |
JP2010150699A (ja) * | 2008-12-25 | 2010-07-08 | Teijin Techno Products Ltd | マルチ細繊度アラミド繊維の製造方法 |
JP5228983B2 (ja) * | 2009-02-19 | 2013-07-03 | 東レ株式会社 | 熱接着用ポリアミドマルチフィラメント |
WO2016076184A1 (fr) | 2014-11-12 | 2016-05-19 | 東レ株式会社 | Multi-filament de polyamide ultra-fin à haute résistance et fil de guipage, bas et tissu l'utilisant |
JP2017020126A (ja) * | 2015-07-08 | 2017-01-26 | 旭化成株式会社 | エアバッグの織物 |
JP6699381B2 (ja) | 2016-06-14 | 2020-05-27 | 東レ株式会社 | ポリアミドマルチフィラメント、その製造方法、エアバッグ用基布およびエアバッグ |
CN109477250B (zh) * | 2016-07-26 | 2021-08-31 | 东丽株式会社 | 聚酰胺复丝和使用它的花边针织物、长筒袜 |
KR102593079B1 (ko) * | 2018-01-25 | 2023-10-24 | 도레이 카부시키가이샤 | 폴리아미드 멀티필라멘트 및 그것을 사용한 레이스 편물 |
KR20190091795A (ko) * | 2018-01-29 | 2019-08-07 | 효성첨단소재 주식회사 | 방탄성능이 향상된 방향족 폴리아미드 섬유의 제조방법 |
JP2020012215A (ja) * | 2018-07-19 | 2020-01-23 | 帝人株式会社 | 導電性パラ型全芳香族ポリアミドマルチフィラメント及びその製造方法 |
-
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- 2021-08-05 CN CN202180049017.4A patent/CN115803484A/zh active Pending
- 2021-08-05 WO PCT/JP2021/029073 patent/WO2022039033A1/fr unknown
- 2021-08-05 JP JP2021551546A patent/JPWO2022039033A1/ja active Pending
- 2021-08-05 EP EP21858180.9A patent/EP4202093A1/fr active Pending
- 2021-08-05 US US18/006,739 patent/US20230279586A1/en active Pending
- 2021-08-18 TW TW110130436A patent/TW202219342A/zh unknown
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CN115803484A (zh) | 2023-03-14 |
TW202219342A (zh) | 2022-05-16 |
US20230279586A1 (en) | 2023-09-07 |
JPWO2022039033A1 (fr) | 2022-02-24 |
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