WO2012039188A1 - Super-high-molecular-weight polyolefin yarn, method for producing same, and drawing device - Google Patents
Super-high-molecular-weight polyolefin yarn, method for producing same, and drawing device Download PDFInfo
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- WO2012039188A1 WO2012039188A1 PCT/JP2011/066397 JP2011066397W WO2012039188A1 WO 2012039188 A1 WO2012039188 A1 WO 2012039188A1 JP 2011066397 W JP2011066397 W JP 2011066397W WO 2012039188 A1 WO2012039188 A1 WO 2012039188A1
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- weight polyolefin
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- 230000008018 melting Effects 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 14
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 6
- 230000000052 comparative effect Effects 0.000 description 26
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- 239000004698 Polyethylene Substances 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 7
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- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
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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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
-
- 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
- D01D5/098—Melt spinning methods with simultaneous stretching
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
- D02J13/001—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass in a tube or vessel
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04C—BRAIDING OR MANUFACTURE OF LACE, INCLUDING BOBBIN-NET OR CARBONISED LACE; BRAIDING MACHINES; BRAID; LACE
- D04C1/00—Braid or lace, e.g. pillow-lace; Processes for the manufacture thereof
- D04C1/06—Braid or lace serving particular purposes
-
- 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
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
- D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
- D10B2321/0211—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene high-strength or high-molecular-weight polyethylene, e.g. ultra-high molecular weight polyethylene [UHMWPE]
-
- 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
-
- 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
- D10B2501/00—Wearing apparel
- D10B2501/04—Outerwear; Protective garments
-
- 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
- D10B2505/00—Industrial
- D10B2505/02—Reinforcing materials; Prepregs
-
- 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
- D10B2509/00—Medical; Hygiene
- D10B2509/04—Sutures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- the present invention relates to an ultra-high molecular weight high-strength polyolefin yarn, a production method thereof, and a drawing apparatus.
- High-strength polyolefin filaments typified by gel-spun ultra-high molecular weight polyethylene filaments are used in ropes, fishing lines, reinforcements, protective clothing, etc. because they are high-strength, lightweight, light-resistant, and excellent in friction resistance.
- ultra-high molecular weight high-strength polyolefin can post-stretch (re-stretch) yarns such as stretched raw yarns, twisted yarn products, and string products.
- Post-stretching is also called re-stretching.
- post-stretching or re-stretching is also simply referred to as “stretching”.
- the melting point of the ultra-high molecular weight high-strength polyolefin is 120 to 240 ° C. depending on the resin type.
- an ultrahigh molecular weight polyethylene has a melting point range of 138 to 162 ° C. The following documents are about polyethylene.
- Patent Document 1 discloses stretching at a melting point or lower (140 to 153 ° C.).
- Patent Document 2 discloses that a braided fishing line is melt-stretched by 1.01 to 2.2 times within a melting point range (150 to 155 ° C.). It is also disclosed that the stretching under such conditions increases the transparency by fusion and becomes a monofilament-like.
- Patent Documents 3, 4, 5 and the like are disclosed with respect to stretching at a higher magnification.
- Patent Document 3 it is disclosed that a forced convection oven is used as a stretching device to stretch at a temperature of 130 to 160 ° C. three times or more.
- Patent Document 4 discloses that the film is stretched by 2.7 times or more at 150 to 157 ° C.
- Patent Document 5 discloses a polyolefin yarn having a single yarn of 0.55 decitex or less obtained by drawing twice or more.
- filaments having a large single yarn fineness and a total fineness are used.
- Patent Document 5 also describes that although the single yarn fineness is thin, it is desirable to stretch the yarn by combining the yarns to increase the total fineness.
- Patent Document 3 a forced convection type oven is used as an example of a stretching apparatus for high-strength polyolefin.
- Patent Document 4 there is no specific description as a stretching device.
- Patent Document 6 relating to a stretching device by the same applicant describes a blow-type stretching device that allows gas to flow at right angles to the yarn.
- the drawing method in which heated gas such as air is blown and circulated in this way is generally used for monofilament drawing and the like.
- the gas flow rate is lowered, the number of circulations per hour decreases, and therefore, temperature distribution unevenness (inlet and outlet, center and end, etc.) in the tank and temperature unevenness over time are likely to occur.
- the total fineness of the yarn and the single yarn fineness are thin, there is a problem that even if the fluctuation is relatively small, yarn breakage or single yarn breakage is likely to occur, and stable drawing is more difficult.
- the present invention provides a production method and a drawing apparatus capable of stably drawing an ultra-high molecular weight high-strength polyolefin yarn even at a high magnification, and a yarn obtained by the production method.
- the ultra high molecular weight polyolefin yarn of the present invention is a stretched ultra high molecular weight polyolefin yarn, which is measured as a maximum peak temperature by a differential scanning calorimeter (DSC) at a temperature rising rate of 20 ° C./min.
- the melting point is present on the higher temperature side than the melting point of the yarn before drawing.
- the method for producing an ultra-high molecular weight polyolefin yarn of the present invention is a method of heating and stretching an ultra-high molecular weight polyolefin yarn, wherein the yarn passage is hollow and a heating liquid is circulated through the jacket portion.
- a tank is installed in a drawing zone, and the yarn is heated and drawn while passing through the passage port in a non-contact manner.
- the drawing apparatus of the present invention is a drawing apparatus for use in the above-described method for drawing an ultra-high molecular weight polyolefin yarn, the means for supplying the yarn, a drawing tank for heating and drawing the yarn, and after drawing
- the drawing tank is characterized in that the yarn passage port is hollow and a heating liquid is circulated in the jacket portion.
- the drawn ultrahigh molecular weight polyolefin yarn of the present invention has a melting point measured as a maximum peak temperature by a differential scanning calorimeter (DSC) at a rate of temperature increase of 20 ° C./min, and the melting point of the yarn before drawing. It has shifted to a higher temperature side. This indicates that the amorphous portion is progressing in the direction of crystallization due to uniform drawing or the crystallization is progressing due to melt recrystallization, and the surface layer of the single fiber and the skin-core structure inside. Indicates that the crystal structure is reduced or disappears, and the crystal structure is changed to a uniform crystal structure in the cross-sectional direction.
- DSC differential scanning calorimeter
- the present invention can stably stretch an ultra-high molecular weight and high-strength polyolefin yarn even at a high magnification, and can obtain an extremely fine drawn yarn having a small total fineness. Furthermore, the present invention can provide an ultrahigh molecular weight polyolefin yarn having a small coefficient of variation in strength and excellent uniformity.
- FIG. 1 is a schematic process diagram of the entire stretching apparatus in one embodiment of the present invention.
- FIG. 2 is a perspective view of a stretching tank in one embodiment of the present invention.
- 3A to 3C are cross-sectional views of the stretching tank in one embodiment of the present invention.
- 4A is a DSC chart of the yarn before drawing in Examples 1 and 4
- FIG. 4B is a DSC chart of the yarn after drawing in Example 1.
- FIG. 5 is a DSC chart of the yarn of Example 4 having a draw ratio of 2.0 times.
- FIG. 6 is a DSC chart of the yarn of Example 4 having a draw ratio of 2.5.
- FIG. 7 is a DSC chart of the yarn of Example 4 having a draw ratio of 3.0.
- FIG. 8 is a DSC chart of the yarn of Example 4 having a draw ratio of 5.6 times.
- FIG. 9 is a DSC chart of the yarn of Comparative Example 4 having a draw ratio of 1.5.
- FIG. 10 is a DSC chart of the yarn of Comparative Example 4 with a draw ratio of 2.0.
- the resulting stretched yarn is subjected to a differential scanning calorimeter (DSC) at a temperature rising rate of 20 ° C./min. It has been found that the melting point measured as the maximum peak temperature when measured in an unconstrained state is shifted to a higher temperature by stretching, and the maximum peak temperature (melting point) is higher than the melting point before stretching.
- DSC differential scanning calorimeter
- the melting point of commercially available high strength polyethylene yarn is about 147 to 153 ° C.
- the drawn yarn of the present invention which has been drawn again, has a maximum peak temperature of 155 to 155 ° C. It was found to be 162 ° C. (high temperature peak).
- the maximum peak temperature is as high as 155 to 162 ° C. when the stretching ratio is high.
- the melting point after stretching is higher than the stretching temperature, suggesting that the ratio of structural change due to stretching is large and the uniformity of the structure is high.
- the component exhibiting a high melting point may be recognized as a small peak or a shoulder in DSC of the raw yarn before drawing, but it is not known that the high melting point component becomes the main peak in the conventional yarn or drawing method. Therefore, the above phenomenon indicates that the crystallization and melt recrystallization of the amorphous part are progressing by uniform stretching, and the surface layer of the single fiber and the internal skin-core structure are reduced or eliminated. This is considered to indicate that the crystal structure is changed to a uniform crystal structure in the cross-sectional direction.
- the crystallinity calculated from the heat of fusion was 72 to 85% after stretching, and a tendency to be equal or slightly increased with respect to the crystallinity before stretching (65 to 80%) was observed. These characteristics are considered to be characteristics that support the temperature control of the present invention with high accuracy and uniform stretching.
- the main peak is 147 to 153 ° C. on the low temperature side even after stretching, and the structural change due to stretching is smaller than the stretching method of the present invention.
- the crystallinity after stretching calculated from the heat of fusion was 70 to 85%.
- ultrahigh molecular weight polyolefin of the present invention examples include polyethylene, polypropylene, polybutene-1, poly (4-methyl-pentene-1), copolymers thereof, and mixtures thereof.
- Ultra-high molecular weight means that the average molecular weight is preferably at least about 200,000, more preferably at least about 600,000 or more.
- the polyolefin yarn of the present invention is preferably a high-strength filament produced by a so-called “gel spinning” method, and a filament having a strength of at least 15 CN / dtex is preferred.
- ultra high molecular weight high strength polyethylene filaments are particularly preferred.
- high-strength polyethylene filaments include trade name “Dyneema” manufactured by Toyobo and DSM, trade name “Spectra” manufactured by Honeywell, and the like.
- the yarn referred to in the present invention is preferably a non-twisted yarn, an entangled yarn, a twisted yarn or a string-made yarn made of multifilament.
- FIG. 1 is a schematic process diagram of the entire stretching apparatus in one embodiment of the present invention.
- FIG. 1 is an example of an overall view of a one-stage stretching apparatus.
- a plurality of (eight in FIG. 1) supply yarns 8 are drawn from the yarn supply device 1 and supplied to the first roller group 2 rotating at a speed V1, heated and stretched in the stretching tank 3, and the second one at a speed V2.
- the drawn yarn 9 is drawn by the two-roller group 4, and the drawn yarn 9 is taken up by the winding device 5.
- the overall draw ratio is represented by V2 / V1.
- the yarn passage port 14 of the drawing tank 3 is hollow, and the yarn is heated and drawn in this portion.
- the heated liquid circulates in the jacket portion 13 surrounded by the stretching tank housing portion 16.
- the circulating liquid is heated to a predetermined temperature by the heating device 6 and forcedly circulated by a pump 7 installed before or after the heating device 6.
- a pump 7 installed before or after the heating device 6.
- FIG. 2 is a perspective view of the stretching tank 3 in one embodiment of the present invention.
- the yarn passing port 14 has a continuous hollow shape, and the supply yarns 10a to 10c are heated and stretched in a non-contact state with the drawing tank 3, and are taken up as drawn yarns 11a to 11c.
- the length L of the drawing tank 3 depends on the yarn speed and the draw ratio, but may be any length as long as the supply yarns 10a to 10c can be heated uniformly and drawn.
- a practically preferable length L of the stretching tank 3 is 0.3 to 10 m, and more preferably 0.5 to 5 m. If the length is too long, uneven temperature tends to occur in the length direction, and it is desirable to connect this unit when necessary.
- 3A to 3C are examples of a cross-sectional view (a cross-sectional view perpendicular to the running direction of the yarn) of the drawing tank 3 in one embodiment of the present invention.
- the drawing tank 3 and the cross section of the yarn passage port 14 are also elliptical.
- the yarns 10a to 10c are heated and drawn without contact with the inner wall portion 12 of the drawing tank.
- a heating fluid circulates in the jacket portion 13.
- the yarn passage port 14 has a continuous hollow shape.
- both the drawing tank 3 and the yarn passage port 14 have a rectangular shape. However, the corners are corrected in an arc shape.
- the drawing tank 3 shown in FIG. 3C has a rectangular (rectangular) shape, and the yarn passage port 14 has a circular shape.
- the short diameter, height or diameter 15 of the yarn passage opening 14 is preferably in the range of 10 to 300 mm, more preferably 10 to 150 mm.
- the heated fluid circulates through a temperature-controlled heating medium heater. Since the heating fluid is not in direct contact with the yarn, it can be circulated at high speed. Further, if the jacket capacity is sufficiently increased with respect to the yarn, the temperature hardly changes due to the running of the yarn.
- a heating fluid Oils normally used as a liquid for heating media can be used preferably. Although not shown, it is desirable to cover the outside of the outer wall of the stretching tank 3 with a heat insulating material.
- positive air blowing means forced air blowing using a fan or the like.
- the drawing method of the present invention has the following advantages over the hot air circulation type drawing that is usually used as a post-drawing method of polyolefin yarn.
- Excellent temperature control accuracy (2) Since there is no positive air blowing, there is an advantage that the yarn path is stable even with a thin filament.
- the yarn is heated by forced circulation of hot air, whereas the present invention mainly includes radiant heat and natural convection from the inner wall, and this difference is considered to be one of the advantages of the present invention.
- the atmosphere temperature (stretching temperature) of the stretching tank is in a temperature range of 150 to 157 ° C. and is controlled within ⁇ 0.2 ° C. More preferably, it is controlled within ⁇ 0.1 ° C. of the atmospheric temperature of the stretching tank (stretching temperature).
- a stable temperature control is possible for the stretching tank of the present invention.
- a conventional blowing type (hot air circulation type) stretching tank a variation of about ⁇ 1.0 ° C. occurs. This is also described in Example 1 in Patent Document 3.
- the heating method of the present invention is considered to have improved temperature accuracy by using liquid as a heating medium and forced circulation.
- the cross-sectional shape of the yarn passage port 14 is illustrated as an ellipse, a rectangle, or a circle in FIGS. 3A to 3C.
- the shape is not limited to this, and may be appropriately designed according to the number of yarns to be drawn. it can.
- the drawing tank is jacket-heated on the entire inner wall other than the inlet and outlet through which the yarn passes.
- a structure having an opening or a gap that is not jacket-heated on the inner wall is not preferable.
- the open / close structure of the stretching tank is not preferable because it takes time to change the temperature by opening and closing and to reach a constant temperature.
- the entrance and exit of the yarn are open, but if the opening area is large, the temperature changes due to the entry and exit of heated air, so that other than the yarn path can be shielded, the entrance front, the exit rear It is preferable to take measures such as providing a heating part at a temperature lower than the temperature keeping or stretching tank temperature to reduce the temperature difference.
- stretching tank unit
- a several tank can be connected as needed, or it can also be set as multistage extending
- the length (L) of the stretching tank refers to the total length of the stretching tank unit.
- a preferable range of the height, diameter or minor axis of the cross section is about 10 to 300 mm. Further, it is desirable that the yarns 10a to 10c pass through the vicinity of the center of the yarn passage opening 14 in terms of uniform heating.
- the yarn used for drawing is a multifilament drawn yarn of ultra-high molecular weight polyolefin.
- a twisted yarn, an entangled yarn, a twisted yarn, or a stringed yarn can be used as the supply drawn yarn.
- raw yarns such as untwisted yarns, entangled yarns, and single-twisted yarns, and then knit and commercialize them, stretch the braided yarns and commercialize them, or use these in combination.
- the raw yarn before stringing can be stretched at a higher magnification.
- These yarns may contain oils such as mineral oil and vegetable oil, waxes, resins such as polyolefin-based, modified polyolefin-based, and ethylene-acrylic acid-based copolymer resins, as necessary.
- the resins can also contain a colorant and the like.
- the thickness (fineness) of the yarn used for drawing is no particular limitation on the thickness (fineness) of the yarn used for drawing, but it is more advantageous for drawing thin yarns than conventional blow-type heating. In this sense, the fineness of the supplied yarn is particularly 400 dtex.
- the following yarns are preferably used.
- an ultrafine yarn of 50 dtex or less which is conventionally difficult to produce as a fineness after drawing, and can be applied to string yarn.
- Such an ultrafine string yarn can be obtained by a method in which the original yarn before stringing is stretched by the stretching method of the present invention and then by stringing, or by a method of stretching by the stretching method of the present invention after stringing, or a combination thereof.
- the single yarn fineness depends on the single yarn fineness of the raw yarn before drawing, if a commercially available yarn having a single yarn fineness of 1.1 dtex is drawn, a super fine yarn of 0.2 dtex or less can be obtained.
- Such thin yarns and string-making yarns are particularly suitable for thin fishing lines.
- it since it is difficult to see with the naked eye and has high strength, it is suitable for hanging strings, sutures, thin knitted fabrics, nets, and the like.
- the temperature is preferably 150 to 157 ° C., and the stretching ratio is about 1.5 to 10 times.
- the temperature is insufficient, the temperature is too short, the temperature is too high, the temperature is too high, and if the time is excessive, it becomes a weak yarn due to melting or excessive fusion.
- the time depends on the temperature and the magnification, the preferred range is 0.1 to 8 minutes.
- the stretching method of the present invention has the following advantages over the conventional hot air circulation heating method. (1) There are few stretch yarn breakage and fluff. (2) The highest drawing ratio is high at the same drawing temperature, and high drawing is possible. (3) Variation in physical properties of drawn yarn is small. (4) High stability during quantitative expansion.
- a tapered string yarn having a thickness ratio of about 1: 5 to 1: 8 can be produced by controlling the stretching ratio to be variable.
- the stretching tank used in Examples 1 to 3 has a length of 3 m and a cross-sectional shape of a hollow rectangle as shown in FIG. 3B, and the single-stage stretching apparatus shown in FIGS. 1 and 2 was used.
- the hot-air circulation type stretching tank of the comparative example was tested by replacing the stretching tank portion of the same length.
- Crystallinity (%) 100 ⁇ ⁇ Hm / ⁇ H
- Example 1 Ultra high molecular weight high-strength polyethylene single strand yarn A that has been stretched in the conventional manner as a supply yarn [Toyobo Co., Ltd., trade name “Dyneema”, 110T-96F (total fineness: 110 Tex, number of filaments: 96)
- the original yarn was subjected to a stretching test using a single twisted (S) yarn of 90 times / m.
- the tensile strength of the used yarn was 31.8 CN / dtex, elongation 4.8%, DSC melting point 150.3 ° C., and crystallinity 75%.
- a DSC chart of the yarn before drawing is shown in FIG. 4A. In FIG.
- a dotted line is an auxiliary line automatically added by the analyzer to obtain the peak area.
- the stretching tank of the used stretching apparatus has a length of 3 m and a cross-sectional shape of a hollow rectangle as shown in FIG. 3B, and a stretching test was performed using the one-stage stretching apparatus shown in FIGS.
- the actually measured temperature of the stretching tank was 154 ⁇ 0.1 ° C., and the temperature was stable.
- the maximum draw ratio was 4.6 times.
- the strength of the drawn yarn at this magnification is 35.7 CN / dtex, the elongation is 2.4%, the DSC melting point is 157.5 ° C., the crystallinity is 80%, and the melting point increases by about 8 ° C. due to drawing. The degree of conversion increased by 5%.
- the DSC chart of the yarn after drawing at the maximum draw ratio of 4.6 times is shown in FIG. 4B.
- Example 1 In place of the drawing tank of Example 1, the same apparatus was used except that a hot air circulation type drawing tank having a length of 3 m was used. As shown in Table 1, winding was possible for 5 minutes or more at a magnification of 3.6 times, but at 3.7 times the yarn breakage occurred in just over 1 minute, and at 3.8 times the yarn breakage occurred frequently. It was impossible to take. Therefore, in the above determination method, the maximum draw ratio was 3.6 times. The strength of the drawn yarn at this magnification was 30.6 CN / dtex, and the elongation was 2.5%. The actually measured temperature of the stretching tank was 154 ⁇ 1.0 ° C. The DSC melting point of the drawn yarn having a draw ratio of 3.6 was 151.5 ° C., and the crystallinity was 79%. The conditions and results of Example 1 and Comparative Example 1 are summarized in Tables 1 and 2.
- Example 1 was able to significantly improve the maximum draw ratio as compared with Comparative Example 1, and accordingly, a drawn yarn with a fineness could be obtained stably.
- the strength of the drawn yarn was also high.
- the melting point measured as the maximum peak temperature measured in a non-restrained condition with a temperature rising rate of 20 ° C./min by a differential scanning calorimeter (DSC) is It was confirmed that it was shifted to a higher temperature side by 8.3 ° C. than the melting point, higher by 7 ° C. and higher in crystallinity than Comparative Example 1.
- Example 2 A draw test was performed using a string yarn B in which four yarns [manufactured by Toyobo Co., Ltd., trade name “Dyneema”, 55T-48F (total fineness: 55 Tex, number of filaments: 48)] as a supply yarn were assembled.
- the used string yarn had a tensile strength of 25.4 CN / dtex and an elongation of 4.9%.
- a stretching test was conducted using the same jacket heating type stretching tank as in Example 1. As shown in Tables 3 and 4, the maximum draw ratio was 3.2 times, which was improved as compared with the comparative example.
- the strength of the drawn yarn at this magnification was 27.0 CN / dtex, and the elongation was 2.9%.
- Comparative Example 2 In the same manner as in Comparative Example 1, the maximum draw ratio was examined using a hot air circulation type drawing tank. As shown in Table 2, the maximum draw ratio was 2.7 times. At 2.9 times, yarn breakage occurred frequently and winding was impossible. The strength of the drawn yarn at this maximum magnification was 26.5 CN / dtex, and the elongation was 3.1%. The conditions and results of Example 2 and Comparative Example 2 are summarized in Tables 3 to 4.
- Example 2 was able to significantly improve the maximum draw ratio as compared with Comparative Example 2, and it was possible to stably obtain a drawn yarn having a fineness corresponding to the maximum draw ratio.
- the melting point measured as the maximum peak temperature measured in a non-restrained state with a differential scanning calorimeter (DSC) at a rate of temperature increase of 20 ° C./min is that of the yarn before drawing. It was confirmed that it was shifted 11.3 ° C. higher than the melting point and 11.1 ° C. higher than that of Comparative Example 2. Furthermore, the degree of crystallinity of Example 2 was higher than that of Comparative Example 2.
- Example 3 Stretched using a relatively thick string yarn C consisting of 8 yarns [made by Toyobo Co., Ltd., trade name “Dyneema”, 165T-144F (total fineness: 165 Tex, number of filaments: 144)] as the supply yarn Tested.
- the string yarn used had a tensile strength of 23.7 CN / dtex and an elongation of 5.9%.
- a stretching test was conducted using the same jacket heating type stretching tank as in Example 1. As shown in Table 3, the maximum draw ratio was 2.4 times, which was improved as compared with the comparative example.
- the strength of the drawn yarn at this magnification was 26.0 CN / dtex, and the elongation was 3.5%.
- Example 3 First, the maximum draw ratio was examined using a hot air circulation type drawing tank in the same manner as in Comparative Example 1. As shown in Table 3, the maximum draw ratio was 2.1 times. The strength of the drawn yarn at this maximum magnification was 25.5 CN / dtex, and the elongation was 3.5%. The conditions and results of Example 3 and Comparative Example 3 are summarized in Tables 5 to 6.
- Example 3 was able to significantly improve the maximum draw ratio as compared with Comparative Example 3, and thus a drawn yarn having a fineness could be stably obtained.
- Table 6 the melting point measured as the maximum peak temperature measured in an unconstrained state at a temperature rising rate of 20 ° C./min by a differential scanning calorimeter (DSC) It was confirmed that it was shifted to the high temperature side by 6.8 ° C. from the melting point, 7 ° C. higher than Comparative Example 3, and high in crystallinity.
- DSC differential scanning calorimeter
- Example 4 comparative example 4
- a quantitative test was performed with eight yarns.
- stretching was performed using two hot-air circulation type stretching tanks.
- the stretching speed was the same as 9 m / min except for the magnification of 5.6 times in this example. (The example of 5.6 times is 4.8 m / min). Since the stretching stability is poor for the comparative example, it is necessary to lower the stretching ratio even in the two-stage process. To obtain the stability for 8 hours at this speed, the stretching ratio was limited to 2 times.
- the stretching method of this example has a main peak at a high temperature even at a low stretching ratio of about 1.5 times, whereas the conventional stretching method (Comparative Example 4, In FIGS. 9 to 10), a peak is recognized on the high temperature side when it is stretched twice, but the main peak temperature is almost the same as that before stretching, and the yarn of this example is also in view of the change in the microstructure of the yarn. It was recognized that there was a difference from the yarn of the conventional drawing method.
- the drawing method of the present invention is clearly characterized in that the maximum draw ratio leading to yarn breakage is high under the same drawing conditions as compared with the drawing method of hot air circulation system heating.
- This has the following advantages in practice. (1) A high-strength polyolefin yarn having a thin yarn with a high draw ratio, which has been difficult in the past, can be obtained. (2) Even when the magnification is the same, thread breakage and fluff are few, the defect rate and loss can be reduced, and the variation in physical properties is also small. (3) Since a cheaper and finer yarn can be used as the supply yarn, the cost of raw materials can be reduced.
- the drawn yarn obtained by the drawing method of the present invention is suitable for ropes, fishing lines, reinforcing materials, protective clothing and the like.
- it since it is difficult to see with the naked eye and has high strength, it is suitable for hanging strings, sutures, thin knitted fabrics, nets, and the like.
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Abstract
Description
(1)温度制御精度に優れる。
(2)積極的な送風をしていないので細いフィラメントでも糸道が安定しているという利点を有する。
(3)また、熱風循環方式では糸の加熱は熱風の強制循環によるのに対し、本発明は内壁からの輻射熱及び自然対流が主体であり、この差も本発明の利点の一つと思われる。 The drawing method of the present invention has the following advantages over the hot air circulation type drawing that is usually used as a post-drawing method of polyolefin yarn.
(1) Excellent temperature control accuracy.
(2) Since there is no positive air blowing, there is an advantage that the yarn path is stable even with a thin filament.
(3) In the hot air circulation system, the yarn is heated by forced circulation of hot air, whereas the present invention mainly includes radiant heat and natural convection from the inner wall, and this difference is considered to be one of the advantages of the present invention.
(1)延伸糸切れ、毛羽が少ない。
(2)同じ延伸温度において最高延倍率が高く高倍率の延伸が可能である。
(3)延伸糸の物性ばらつきが小さい。
(4)量的拡大時の安定性が高い。 The stretching method of the present invention has the following advantages over the conventional hot air circulation heating method.
(1) There are few stretch yarn breakage and fluff.
(2) The highest drawing ratio is high at the same drawing temperature, and high drawing is possible.
(3) Variation in physical properties of drawn yarn is small.
(4) High stability during quantitative expansion.
<物性試験>
強伸度はJIS L1013の測定方法に準じた。繊度は糸を1mにカットし重量を0.1mg単位で測定し、10000倍して繊度(デシテックス:dtex)を求めた。
<延伸性評価>
各延伸条件において延伸性を下記の基準で判定した。
A:5分間以上糸切れ発生なし。
B:巻き取り可能であったが5分間以内で糸切れ発生した。
C:直ちに糸切れして巻き取り不可
<示差走査熱量計(DSC)による融点及び結晶化度の測定>
株式会社島津製作所社製の示差走査熱量計DSC-60型を用い、昇温速度20℃/分で糸を無拘束の状態で測定した。融解吸熱ピークに於ける最大ピークの温度を融点とした。また、ピーク面積から求められる吸熱量ΔHm(J/g)から次式により結晶化度を求めた。
結晶化度(%)=100×ΔHm/ΔH
ここでΔHは完全結晶での融解熱量であり、ポリエチレンの場合ΔH=293J/gとして計算した。サンプルが製紐、樹脂加工などで糸が拘束状態と思われるものはほぐしてから測定に供した。 Evaluation in Examples and Comparative Examples was performed by the following methods.
<Physical property test>
The strength and elongation were in accordance with the measuring method of JIS L1013. The fineness was obtained by cutting the yarn into 1 m, measuring the weight in units of 0.1 mg, and multiplying it by 10,000 to obtain the fineness (dtex).
<Extendability evaluation>
Under each stretching condition, the stretchability was determined according to the following criteria.
A: No yarn breakage for 5 minutes or more.
B: Although winding was possible, thread breakage occurred within 5 minutes.
C: Thread breakage immediately and unwinding <Measurement of melting point and crystallinity by differential scanning calorimeter (DSC)>
Using a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation, the yarn was measured in an unconstrained state at a heating rate of 20 ° C./min. The temperature at the maximum peak in the melting endothermic peak was defined as the melting point. Further, the degree of crystallinity was obtained from the endothermic amount ΔHm (J / g) obtained from the peak area by the following equation.
Crystallinity (%) = 100 × ΔHm / ΔH
Here, ΔH is the heat of fusion in a complete crystal, and was calculated as ΔH = 293 J / g in the case of polyethylene. Samples that were made of string, resin processing, etc., where the yarn was considered to be in a restrained state, were loosened and subjected to measurement.
<延伸前原糸>
原糸A:東洋紡績社製、商品名「ダイニーマ」、110T-96F-410 片撚り(S)90回/m
製紐糸B:東洋紡績社製、商品名「ダイニーマ」、55T-48F-410 4本組
製紐糸C:東洋紡績社製、商品名「ダイニーマ」、165T-144F-410 8本組 The following yarns were used as raw yarns before drawing.
<Original yarn before drawing>
Raw yarn A: manufactured by Toyobo Co., Ltd., trade name “Dyneema”, 110T-96F-410, single twist (S) 90 times / m
Made of string yarn B: manufactured by Toyobo Co., Ltd., trade name “Dyneema”, 55T-48F-410, 4-piece set Made of string yarn C: manufactured by Toyobo Co., Ltd., trade name “Dyneema”, 165T-144F-410, 8 pieces
供給糸条として従来法の延伸がなされている超高分子量高強度ポリエチレン片撚り原糸A[東洋紡績社製、商品名「ダイニーマ」、110T-96F(トータル繊度:110Tex、フィラメント数:96本)の原糸を片撚り(S)90回/m掛けた糸条]を用いて延伸試験した。使用した原糸の引張強度は31.8CN/dtex、伸度4.8%、DSC融点150.3℃、結晶化度75%であった。延伸前の糸条のDSCチャートを図4Aに示す。図4Aにおいて、点線はピーク面積を求めるために分析装置が自動的に加えた補助線である。これは以下のDSCチャートでも同一である。使用した延伸装置の延伸槽は長さが3m、断面形状が図3Bに示したような中空長方形で、図1及び図2に示した1段延伸装置を用いて延伸試験した。延伸槽の実測温度は154±0.1℃であり、温度は安定していた。延伸倍率を3.6~4.7倍で試験した結果、表1に示したように最高延伸倍率は4.6倍であった。この倍率における延伸糸の強度は35.7CN/dtex、伸度は2.4%、DSC融点は157.5℃、結晶化度は80%であり、融点は延伸により約8℃上昇し、結晶化度は5%増加した。最高延伸倍率4.6倍における延伸後の糸条のDSCチャートを図4Bに示す。 Example 1
Ultra high molecular weight high-strength polyethylene single strand yarn A that has been stretched in the conventional manner as a supply yarn [Toyobo Co., Ltd., trade name “Dyneema”, 110T-96F (total fineness: 110 Tex, number of filaments: 96) The original yarn was subjected to a stretching test using a single twisted (S) yarn of 90 times / m. The tensile strength of the used yarn was 31.8 CN / dtex, elongation 4.8%, DSC melting point 150.3 ° C., and crystallinity 75%. A DSC chart of the yarn before drawing is shown in FIG. 4A. In FIG. 4A, a dotted line is an auxiliary line automatically added by the analyzer to obtain the peak area. This is the same in the following DSC charts. The stretching tank of the used stretching apparatus has a length of 3 m and a cross-sectional shape of a hollow rectangle as shown in FIG. 3B, and a stretching test was performed using the one-stage stretching apparatus shown in FIGS. The actually measured temperature of the stretching tank was 154 ± 0.1 ° C., and the temperature was stable. As a result of testing at a draw ratio of 3.6 to 4.7 times, as shown in Table 1, the maximum draw ratio was 4.6 times. The strength of the drawn yarn at this magnification is 35.7 CN / dtex, the elongation is 2.4%, the DSC melting point is 157.5 ° C., the crystallinity is 80%, and the melting point increases by about 8 ° C. due to drawing. The degree of conversion increased by 5%. The DSC chart of the yarn after drawing at the maximum draw ratio of 4.6 times is shown in FIG. 4B.
実施例1の延伸槽に換えて、長さ3mの熱風循環方式の延伸槽を用いた以外は同一の装置を用いて、倍率を上げながら3本の糸で一段延伸の試験をした。表1に示したように、倍率3.6倍では5分以上巻取り可能であったが、3.7倍では1分強で糸切れ発生し、3.8倍では糸切れ多発して巻取り不能であった。したがって前記の判定方法で最高延伸倍率は3.6倍であった。この倍率における延伸糸の強度は30.6CN/dtex、伸度は2.5%であった。延伸槽の実測温度は154±1.0℃であった。延伸倍率3.6の延伸糸のDSC融点は151.5℃、結晶化度は79%であった。実施例1及び比較例1の条件と結果をまとめて表1~表2に示す。 (Comparative Example 1)
In place of the drawing tank of Example 1, the same apparatus was used except that a hot air circulation type drawing tank having a length of 3 m was used. As shown in Table 1, winding was possible for 5 minutes or more at a magnification of 3.6 times, but at 3.7 times the yarn breakage occurred in just over 1 minute, and at 3.8 times the yarn breakage occurred frequently. It was impossible to take. Therefore, in the above determination method, the maximum draw ratio was 3.6 times. The strength of the drawn yarn at this magnification was 30.6 CN / dtex, and the elongation was 2.5%. The actually measured temperature of the stretching tank was 154 ± 1.0 ° C. The DSC melting point of the drawn yarn having a draw ratio of 3.6 was 151.5 ° C., and the crystallinity was 79%. The conditions and results of Example 1 and Comparative Example 1 are summarized in Tables 1 and 2.
供給糸条として原糸[東洋紡績社製、商品名「ダイニーマ」、55T-48F(トータル繊度:55Tex、フィラメント数:48本)]を4本組した製紐糸Bを用いて延伸試験した。使用した製紐糸の引張強度は25.4CN/dtex、伸度4.9%であった。実施例1と同じジャケット加熱方式の延伸槽を用いて延伸試験した。表3及び表4に示したように最高延伸倍率は3.2倍で比較例にくらべ向上した。この倍率における延伸糸の強度は27.0CN/dtex、伸度は2.9%であった。 (Example 2)
A draw test was performed using a string yarn B in which four yarns [manufactured by Toyobo Co., Ltd., trade name “Dyneema”, 55T-48F (total fineness: 55 Tex, number of filaments: 48)] as a supply yarn were assembled. The used string yarn had a tensile strength of 25.4 CN / dtex and an elongation of 4.9%. A stretching test was conducted using the same jacket heating type stretching tank as in Example 1. As shown in Tables 3 and 4, the maximum draw ratio was 3.2 times, which was improved as compared with the comparative example. The strength of the drawn yarn at this magnification was 27.0 CN / dtex, and the elongation was 2.9%.
比較例1と同様にして熱風循環方式の延伸槽を用いて最高延伸倍率を調べた。表2に示したように、最高延伸倍率は2.7倍であった。2.9倍では糸切れ多発して巻取り不能であった。この最高倍率における延伸糸の強度は26.5CN/dtex、伸度は3.1%であった。実施例2及び比較例2の条件と結果をまとめて表3~表4に示す。 (Comparative Example 2)
In the same manner as in Comparative Example 1, the maximum draw ratio was examined using a hot air circulation type drawing tank. As shown in Table 2, the maximum draw ratio was 2.7 times. At 2.9 times, yarn breakage occurred frequently and winding was impossible. The strength of the drawn yarn at this maximum magnification was 26.5 CN / dtex, and the elongation was 3.1%. The conditions and results of Example 2 and Comparative Example 2 are summarized in Tables 3 to 4.
供給糸条として原糸[東洋紡績社製、商品名「ダイニーマ」、165T-144F(トータル繊度:165Tex、フィラメント数:144本)]を8本組した比較的太い製紐糸Cを用いて延伸試験した。使用した製紐糸の引張強度は23.7CN/dtex、伸度は5.9%であった。実施例1と同じジャケット加熱方式の延伸槽を用いて延伸試験した。表3に示したように最高延伸倍率は2.4倍で比較例にくらべ向上した。この倍率における延伸糸の強度は26.0CN/dtex、伸度は3.5%であった。 (Example 3)
Stretched using a relatively thick string yarn C consisting of 8 yarns [made by Toyobo Co., Ltd., trade name “Dyneema”, 165T-144F (total fineness: 165 Tex, number of filaments: 144)] as the supply yarn Tested. The string yarn used had a tensile strength of 23.7 CN / dtex and an elongation of 5.9%. A stretching test was conducted using the same jacket heating type stretching tank as in Example 1. As shown in Table 3, the maximum draw ratio was 2.4 times, which was improved as compared with the comparative example. The strength of the drawn yarn at this magnification was 26.0 CN / dtex, and the elongation was 3.5%.
まず、比較例1と同様にして熱風循環方式の延伸槽を用いて最高延伸倍率を調べた。表3に示したように、最高延伸倍率は2.1倍であった。この最高倍率における延伸糸の強度は25.5CN/dtex、伸度は3.5%であった。実施例3及び比較例3の条件と結果をまとめて表5~表6に示す。 (Comparative Example 3)
First, the maximum draw ratio was examined using a hot air circulation type drawing tank in the same manner as in Comparative Example 1. As shown in Table 3, the maximum draw ratio was 2.1 times. The strength of the drawn yarn at this maximum magnification was 25.5 CN / dtex, and the elongation was 3.5%. The conditions and results of Example 3 and Comparative Example 3 are summarized in Tables 5 to 6.
延伸装置として実施例1の延伸槽を2台使用した2段延伸装置を使用して、8本の糸で量的試験を実施した。比較として熱風循環方式の延伸槽を同様に2台使用した延伸を行った。延伸性の評価として実施例1~3及び比較例1~3では5分間に対し、8時間運転での状態を評価した。結果を表7に示した。延伸速度は本実施例の倍率5.6倍を除き9m/分と同じとした。(5.6倍の例は4.8m/分)。比較例については延伸安定性が悪いため、2段加工としても、延伸倍率を下げる必要があり、この速度で8時間の安定性を得るためには延伸倍率は2倍が限界であったが、本実施例の延伸方法では2.5倍で問題なく、延伸速度を落とした場合、延伸倍率は5.6倍でも糸切れなく延伸可能であった。また強度のばらつき(変動係数)についても本実施例品が良好であった。延伸倍率を変えた延伸後サンプルを採取し、DSC測定を行った結果を表8に示した。DSCチャートは図5~10に示す。 (Example 4, comparative example 4)
Using a two-stage drawing apparatus using two drawing tanks of Example 1 as a drawing apparatus, a quantitative test was performed with eight yarns. For comparison, stretching was performed using two hot-air circulation type stretching tanks. As the evaluation of stretchability, in Examples 1 to 3 and Comparative Examples 1 to 3, the state in an 8-hour operation was evaluated for 5 minutes. The results are shown in Table 7. The stretching speed was the same as 9 m / min except for the magnification of 5.6 times in this example. (The example of 5.6 times is 4.8 m / min). Since the stretching stability is poor for the comparative example, it is necessary to lower the stretching ratio even in the two-stage process. To obtain the stability for 8 hours at this speed, the stretching ratio was limited to 2 times. In the drawing method of this example, there was no problem at 2.5 times, and when the drawing speed was lowered, even if the draw ratio was 5.6 times, the drawing was possible without breakage. The product of this example was also good in terms of variation in strength (coefficient of variation). Table 8 shows the results of taking a sample after stretching with the stretching ratio changed and performing DSC measurement. DSC charts are shown in FIGS.
(1)従来困難であった高延伸倍率の細い糸条の高強度ポリオレフィン糸条が得られる。
(2)同じ倍率でも糸切れ、毛羽発生が少なく、不良率、ロスの低減が可能で物性のバラツキも小さい。
(3)供給糸条としてより安価な太繊度の糸条を使用できるので、原材料費のコストダウンが可能である。 From the above, the drawing method of the present invention is clearly characterized in that the maximum draw ratio leading to yarn breakage is high under the same drawing conditions as compared with the drawing method of hot air circulation system heating. This has the following advantages in practice.
(1) A high-strength polyolefin yarn having a thin yarn with a high draw ratio, which has been difficult in the past, can be obtained.
(2) Even when the magnification is the same, thread breakage and fluff are few, the defect rate and loss can be reduced, and the variation in physical properties is also small.
(3) Since a cheaper and finer yarn can be used as the supply yarn, the cost of raw materials can be reduced.
2 第1ローラー群
3 延伸槽
4 第2ローラー群
5 巻き取り装置
6 循環液体の加熱装置
7 ポンプ
8,10a~10c 供給糸条
9,11a~11c 延伸糸条
12 延伸槽内壁部
13 ジャケット部
14 糸条の通過口
15 糸条の通過口の短径、高さ又は直径
16 延伸槽ハウジング部 DESCRIPTION OF SYMBOLS 1 Yarn supply apparatus 2
Claims (17)
- 延伸された超高分子量ポリオレフィン糸条であって、
示差走査熱量計(DSC)により昇温速度20℃/分の条件で、無拘束状態で測定した最大ピーク温度として測定される融点が、延伸前の糸条の融点より高温側に存在していることを特徴とする超高分子量ポリオレフィン糸条。 Stretched ultra high molecular weight polyolefin yarn,
The melting point measured as the maximum peak temperature measured in a non-restrained state under the condition of a heating rate of 20 ° C./min by a differential scanning calorimeter (DSC) exists on the higher temperature side than the melting point of the yarn before drawing. Ultra high molecular weight polyolefin yarn characterized by that. - 前記延伸された超高分子量ポリオレフィン糸条の融点は延伸前の糸条の融点より5℃以上高温側に存在している請求項1に記載の超高分子量ポリオレフィン糸条。 2. The ultrahigh molecular weight polyolefin yarn according to claim 1, wherein the drawn ultrahigh molecular weight polyolefin yarn has a melting point of 5 ° C. or more higher than the melting point of the yarn before drawing.
- 前記延伸された超高分子量ポリオレフィン糸条の総繊度は50dtex以下、強度の変動係数は2%以下である請求項1又は2に記載の超高分子量ポリオレフィン糸条。 The ultrahigh molecular weight polyolefin yarn according to claim 1 or 2, wherein the stretched ultra high molecular weight polyolefin yarn has a total fineness of 50 dtex or less and a coefficient of variation of strength of 2% or less.
- 前記超高分子量ポリオレフィンが超高分子量ポリエチレンである請求項1~3のいずれか1項に記載の超高分子量ポリオレフィン糸条。 The ultrahigh molecular weight polyolefin yarn according to any one of claims 1 to 3, wherein the ultrahigh molecular weight polyolefin is ultrahigh molecular weight polyethylene.
- 前記延伸された超高分子量ポリエチレン糸条は、示差走査熱量計(DSC)で昇温速度20℃/分の条件で無拘束状態で測定した最大融解ピーク温度が155~162℃である請求項4に記載の超高分子量ポリオレフィン糸条。 5. The drawn ultrahigh molecular weight polyethylene yarn has a maximum melting peak temperature of 155 to 162 ° C. measured in a non-restrained state with a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min. The ultra high molecular weight polyolefin yarn described in 1.
- 前記延伸された超高分子量ポリエチレン糸条は、示差走査熱量計(DSC)で昇温速度20℃/分の条件において、無拘束状態で測定した融解熱から求められた結晶化度が76~85%である請求項4又は5に記載の超高分子量ポリオレフィン糸条。 The stretched ultrahigh molecular weight polyethylene yarn has a crystallinity of 76 to 85 determined from the heat of fusion measured in an unconstrained state at a temperature increase rate of 20 ° C./min with a differential scanning calorimeter (DSC). The ultrahigh molecular weight polyolefin yarn according to claim 4 or 5, which is%.
- 超高分子量ポリオレフィン糸条を加熱延伸する方法であって、
糸条の通過口は中空で、ジャケット部には加熱液体が循環している延伸槽を延伸ゾーンに設置し、
前記糸条を非接触で、前記通過口を通過させながら加熱、延伸することを特徴とする超高分子量ポリオレフィン糸条の製造方法。 A method of heating and drawing an ultrahigh molecular weight polyolefin yarn,
The yarn passage is hollow and the jacket is installed in the drawing zone with a drawing tank in which heated liquid is circulated.
A method for producing an ultrahigh molecular weight polyolefin yarn, wherein the yarn is heated and stretched while passing through the passage opening in a non-contact manner. - 前記糸条通過口では積極的な送風を行わず、ジャケット部からの輻射熱及び自然対流により糸条を加熱する請求項7に記載の超高分子量ポリオレフィン糸条の製造方法。 The method for producing an ultrahigh molecular weight polyolefin yarn according to claim 7, wherein the yarn is heated by radiant heat from the jacket portion and natural convection without actively blowing air at the yarn passage opening.
- 前記延伸槽の雰囲気温度が150~157℃、延伸倍率が1.5~10倍である請求項7又は8に記載の超高分子量ポリオレフィン糸条の製造方法。 The method for producing an ultrahigh molecular weight polyolefin yarn according to claim 7 or 8, wherein the atmospheric temperature of the drawing tank is 150 to 157 ° C and the draw ratio is 1.5 to 10 times.
- 前記延伸槽の雰囲気温度が150~157℃の温度範囲であり、かつ±0.2℃以内に制御されている請求項7~9のいずれか1項に記載の超高分子量ポリオレフィン糸条の製造方法。 The production of the ultrahigh molecular weight polyolefin yarn according to any one of claims 7 to 9, wherein an atmospheric temperature of the drawing tank is in a temperature range of 150 to 157 ° C and is controlled within ± 0.2 ° C. Method.
- 前記延伸前の糸条は、無撚り糸、交絡糸、撚糸又は製紐糸である請求項7~10のいずれか1項に記載の超高分子量ポリオレフィン糸条の製造方法。 The method for producing an ultrahigh molecular weight polyolefin yarn according to any one of claims 7 to 10, wherein the yarn before drawing is a non-twisted yarn, an entangled yarn, a twisted yarn or a string yarn.
- 前記延伸前の糸条の繊度は400dtex以下であることを請求項7~11のいずれか1項に記載の超高分子量ポリオレフィン糸条の製造方法。 The method for producing an ultrahigh molecular weight polyolefin yarn according to any one of claims 7 to 11, wherein the fineness of the yarn before drawing is 400 dtex or less.
- 製紐前原糸を請求項7~12のいずれか1項に記載の延伸方法で延伸後、この延伸糸を少なくとも一部を用いて製紐することを特徴とする超高分子量ポリオレフィン糸条の製造方法。 An ultra-high-molecular-weight polyolefin yarn, characterized in that the pre-string yarn is drawn by the drawing method according to any one of claims 7 to 12 and then drawn using at least a part of the drawn yarn. Method.
- 製紐前原糸を請求項7~13のいずれか1項に記載の延伸方法で延伸後、この延伸糸を少なくとも一部を用いて製紐し、製紐糸をさらに延伸することを特徴とする超高分子量ポリオレフィン糸条の製造方法。 The raw yarn before string making is drawn by the drawing method according to any one of claims 7 to 13, and then the drawn yarn is stringed using at least a part thereof, and the string yarn is further drawn. Method for producing ultra high molecular weight polyolefin yarn.
- 請求項7~14のいずれか1項に記載の超高分子量ポリオレフィン糸条の製造方法に使用するための延伸装置であって、
糸条を供給する手段と、
前記糸条を加熱延伸する延伸槽と、
延伸後の糸条を巻き取る手段を備え、
前記延伸槽は、前記糸条の通過口は中空でジャケット部には加熱液体が循環していることを特徴とする延伸装置。 A drawing apparatus for use in the method for producing an ultrahigh molecular weight polyolefin yarn according to any one of claims 7 to 14,
Means for supplying yarn,
A drawing tank for heating and drawing the yarn;
Equipped with a means for winding the stretched yarn,
The drawing apparatus is characterized in that the yarn passing port is hollow and a heating liquid is circulated in the jacket portion. - 前記加熱液体は前記延伸槽の外で加熱され、ポンプにより循環されている請求項15に記載の延伸装置。 The stretching apparatus according to claim 15, wherein the heated liquid is heated outside the stretching tank and is circulated by a pump.
- 前記糸条通過口の高さ又は直径が5~300mm、前記延伸槽の長さが0.3~10mの範囲である請求項15又は16に記載の延伸装置。 The stretching apparatus according to claim 15 or 16, wherein the yarn passage opening has a height or diameter of 5 to 300 mm and a length of the stretching tank of 0.3 to 10 m.
Priority Applications (4)
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JP2012509407A JP5001472B2 (en) | 2010-09-21 | 2011-07-20 | Ultra high molecular weight polyolefin yarn, method for producing the same and drawing device |
KR1020127029467A KR101849796B1 (en) | 2010-09-21 | 2011-07-20 | Super-high-molecular-weight polyolefin yarn, method for producing same, and drawing device |
CN201180024214.7A CN103097596A (en) | 2010-09-21 | 2011-07-20 | Super-high-molecular-weight polyolefin yarn, method for producing same, and drawing device |
US13/813,297 US20130130029A1 (en) | 2010-09-21 | 2011-07-20 | Super-high-molecular-weight polyolefin yarn, method for producing same, and drawing device |
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JP2010-210887 | 2010-09-21 | ||
JP2010210887 | 2010-09-21 |
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PCT/JP2011/066397 WO2012039188A1 (en) | 2010-09-21 | 2011-07-20 | Super-high-molecular-weight polyolefin yarn, method for producing same, and drawing device |
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US (1) | US20130130029A1 (en) |
JP (1) | JP5001472B2 (en) |
KR (1) | KR101849796B1 (en) |
CN (1) | CN103097596A (en) |
TW (1) | TW201215719A (en) |
WO (1) | WO2012039188A1 (en) |
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JP5696808B1 (en) * | 2014-03-28 | 2015-04-08 | 東洋紡株式会社 | Multifilament |
JP5696809B1 (en) * | 2014-03-28 | 2015-04-08 | 東洋紡株式会社 | Multifilament |
JP2016508549A (en) * | 2013-01-25 | 2016-03-22 | ディーエスエム アイピー アセッツ ビー.ブイ. | Method for producing drawn multifilament yarn |
CN105839200A (en) * | 2016-03-18 | 2016-08-10 | 上海化工研究院 | Suspension fluid uniform charging method and device |
JP2019031754A (en) * | 2017-08-07 | 2019-02-28 | 株式会社ゴーセン | Ultrahigh molecular weight polyethylene multifilament fusible yarn and manufacturing method thereof |
JP2021050464A (en) * | 2021-01-08 | 2021-04-01 | 株式会社ゴーセン | Method for producing ultrahigh-molecular weight polyethylene multifilament fusible yarn |
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- 2011-07-20 CN CN201180024214.7A patent/CN103097596A/en active Pending
- 2011-07-20 US US13/813,297 patent/US20130130029A1/en not_active Abandoned
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KR101849796B1 (en) | 2018-04-17 |
CN103097596A (en) | 2013-05-08 |
KR20130096634A (en) | 2013-08-30 |
TW201215719A (en) | 2012-04-16 |
US20130130029A1 (en) | 2013-05-23 |
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JPWO2012039188A1 (en) | 2014-02-03 |
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