CA1204260A - Polypropylene fibers having improved heat- shrinkability and tenacity - Google Patents
Polypropylene fibers having improved heat- shrinkability and tenacityInfo
- Publication number
- CA1204260A CA1204260A CA000435884A CA435884A CA1204260A CA 1204260 A CA1204260 A CA 1204260A CA 000435884 A CA000435884 A CA 000435884A CA 435884 A CA435884 A CA 435884A CA 1204260 A CA1204260 A CA 1204260A
- Authority
- CA
- Canada
- Prior art keywords
- polypropylene
- ratio
- shrinkability
- heat
- tenacity
- 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.)
- Expired
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—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
- D01F6/06—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 from polypropylene
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/28—Stretching filaments in gas or steam
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/73—Processes of stretching
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Polypropylene fibers having a much improved percentage heat shrinkage and also an improved tenacity are provided, which fibers comprise a polypropylene resin having a density of 0.905 or more, an isotactic pentad ratio of boiling n-heptane-insoluble portion (P0) of 0.960 or more and a ratio of pentad having two different kinds of configurations (P2), of 0.002 (0.2%) or less.
Polypropylene fibers having a much improved percentage heat shrinkage and also an improved tenacity are provided, which fibers comprise a polypropylene resin having a density of 0.905 or more, an isotactic pentad ratio of boiling n-heptane-insoluble portion (P0) of 0.960 or more and a ratio of pentad having two different kinds of configurations (P2), of 0.002 (0.2%) or less.
Description
~204'~60 Polypropylene fibers having improved heat-shrinkability and tenacity BACKGROUND OF THE INVENTION
1. Field of the Invention This invention relates to polypropylene fibers having an improved heat-shrinkability and tenacity.
More particularly it relates to polypropylene fibers produced from a specified polypropylene resin and having an improved tenacity and an improved shrinkability in a heated atmosphere.
1. Field of the Invention This invention relates to polypropylene fibers having an improved heat-shrinkability and tenacity.
More particularly it relates to polypropylene fibers produced from a specified polypropylene resin and having an improved tenacity and an improved shrinkability in a heated atmosphere.
2. Description of the Prior Art In general, fibers consisting of polypropylene resin have been first prepared by melt-extruding the resin through various shapes of die, then processed into filaments, staple fibers, flat yarns, etcO via stretching step, heat-treatment step, etc., and further secondarily processed into waddings, carpet piles, non-woven fabrics, industrial materials, striped fabrics, cloth-like products, etc.
Fibers consisting of polypropylene resin have suitable tenacity characteristics imparted by orientation-crystallization during their spinning and stretching steps and have been used for practical uses, but they have such drawbacks that their tenacity is liable to be reduced and their shrinkage is liable to occur.
~Z14Z60 Thus in order to prevent shrinkage of their products with increase of time when they are preserved and used at room temperature, the fibers have been usually subjected to relaxation heat treatment at a temperature lower than the melting point of polypropylene after their stretching, to remove their internal strain formed when they are oriented during the spinning and stretching steps, i.e. their residual stress, which is a cause of the shrinkage and promote recrystallization to thereby stabilize the shrinkage. On the other hand, in order to make up the fibers into products, various secondary processings are required, and in the case of some products, the fibers are often subjected to various processes - exposed to an atmosphere at higher temperatures than room temperature; in particular, at higher temperatures than the heat treatment temperature, there occurs retrogradation of the orientation at the time of spinning and stretching whereby the shrinkage is rapidly increased.
Referring to flat yarns used as a primary backing of carpets, for example in the case of tufted carpets, polypropylene fibers are tufted on the backing and backed with a latex, followed by a latex-drying step; hence the fibers are exposed to a heated atmosphere at considerably high temperatures. Further, recently there is a tendency that the latex-drying step is carried lZI:)4Z60 out at higher temperatures and higher speeds to improve the productivity of the products. For example, when the fibers are allowed to stand at 130C for 15 minutes, if they have a heat-shrinkability endurable to the conditions, no problem has so far been raised, but a heat-shrinkability endurable to higher temperatures than such a temperature has recently come to be required.
In order to obtain a low heat-shrinkability under heating, i.e. the so-called low shrinkage, relaxation annealing may be generally applied after stretching, as described above, but the percentage relaxation has so far been generally 10 to 25%; if the percentage exceeds such values, a problem is raised that the productivity is reduced as much as the increase in the pexcentage relaxation.
Further, the percentage heat shrinkage of flat yarns is said to depend on the shrinkage of their non-crystallized portion caused by crystallization under heating, the recovery of the internal strain formed at the time of orientation by stretching and the retrogradation of the orientation. Thus, there has been employed a process of crystallizing the film prior to stretching as much as possible or subjecting the film after stretched to relaxation annealing to thereby effect removal of the internal strain and recrystallization.
12~4Z60 As for the process for advancing the crystallization of the film prior to stretching, as far as the aspect of processing is concerned, slow cooling is suitable for cooling the film just after extruded; hence air cooling manner is more advantageous than water cooling manner, and in the case of water cooling manner, cooling has been advantageiously carried out at a relatively high temperature of water. As far as the aspect of raw material is concerned, as for a process for enhancing the crystallization of the film or unstretched yarns, there has been employed a process of adding an organic neueleus-creating agent such as p-tertiary-butyl benzoic acid aluminum salt, dibenzylidene sorbitol, etc. to a conventional polypropylene resin . However, even though the above-mentioned processes are employed and further a relaxation annealing is added thereto, improvement in the heat-shrinkability at high temperatures, higher than 130C cannot be observed.
SUMMARY OF THE INVENTION
The obje~t of the present invention is to provide polypropylene fibers having a superior heat-shrinkability and excellent mechanical properties such as tenacity.
The present inventors have made strenuous studies on the above-mentioned problems, and have found that when a polypropylene having a density of 0.905 or more, 12~4260 an isotactic pentad ratio of boiling n-heptane-insoluble portion (Po) of 0~960 or more and a ratio of pentad having two different kinds of configurations (P2), of 0.002 or less is used as the raw material for polypropylene fibers, it is possible to improve the heat-shrinkability of the polypropylene fibers in the direction in which it is reduced to a large extent.
The present invention resides in Polyplopylene fibers having an improved heat-shrinkability and tenacity, which comprise a polypropylene resin having a density of 0.905 or more, an isotactic pentad ratio of boiling n-heptane-insoluble portion (Po) of 0.960 or more and a ratio of pentad having two different kinds of configurations tP2), of 0.002 (0.2%) or less.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows a laterally - cross-sectional view of an example of connected yarns.
Fig. 2 shows a laterally cross-sectional view of an example of ribbed tapes.
Fig. 3 shows a view of percentages heat shrinkage of flat yarns obtained in Example 1 and Comparative example 1, at various temperatures.
Fig. 4 shows a view of percentages heat shrinkage of stretched yarns obtained in Example 6 and Comparative example 5, at various temperatures.
1~4260 Fig. 5 shows a view illustrating the rel.ationship between the stretch ratio and tenaci.ty of stretched yarns o~tained in Example 6 and Comparative example 5.
DETAI:LED DESCRIPTION OF THE INVENTION
Polypropylene used in the present invention can be prepared according to the process described in the s.pecification of Japanese laid-open patent publication No. 58-104907, by polymeri~ing propylene in the presence of a catalyst prepared by reacting an organoaluminum compound or a reaction product of an organoaluminum compound with an electron donor, with TiCQ4., further reacting the resulting solid product ~II) with an electron donor and an electron acceptor, and then combining the resulting solid product ~III) with an organoaluminum compound and an aromatic carboxylic acid ester (V), the molar ratio of (V) to ~III) being 0.2 to 10Ø
Isotactic pentad.ratio referred to herein means an isotactic pentad ratio in terms of pentad units in the molecular chain of polypropylene, measured by using 13C-NMR (see A. Zambelli et al~ Macromolecules 6, 925 (1973)). In other words, the isotactic pentad ratio refers to a ratio of five continuously and isotactically connected propylene monomer.units in total propylene monomer units.
,i~ .
~Z042~0 The peak-assigning method in the above measurement by means of NMR was carried out based on Macromolecules 8,687 (1975)~ In addition, the measurement by means of NMR was carried out by using an apparaths of FT-5 NMR at 270 MHZ, and by improving th~ signal detectionlimit up to an isotactic pentad ratio of 0.001, by an integrating measurement of 27,000 times.
As to pentad, (1) an isotactic pentad is expressed by mmmm (00000) or (11111); (2) a pentad having one different kinds of configuration is expressed by either one of mmmr (00001) or (11110), mmrr (00010) or (11101), or mrrm (00100) or (11011); and (3) a pentad having two different kinds of configurations is expressed by mmrm (00011) or (11100), mrrr (00101) or (11010), mrmr (00110) or (11001), rrmr (01001~ or (10110), rrrr (01010) or (10101~ or rmmr (01110) or (10001), wherein m represents an isotactic dyad; r represents a syndiotactic dyad; and 0 and 1 each represents an individual monomer unit configuration along the polymer chain, and 0 represents a configuration while 1 represents a reverse configuration.
. 7 --lZ04Z60 The boiling n-heptane-insoluble portion of polypropylene used in the present invention refers to an extraction residue obtained by wholely dissolving 5g of polypropylene in 500ml of boiling xylene, pouring the solution in 5Q of methanol, recovering the resulting precipitate, drying it and extracting it with boiling n-heptane by means of a Soxhlet extractor for 6 hours. The density was determined by preparing a sample according to the press m~thod of JIS K 6758 and measuring it according to the underwater replacement method of JIS K 7112.
A polypropylene having an isotactic pentad ratio of boiling n-heptane-insoluble portion (P0) less than 0.~60 is insuffici~n~ i~ th~ effect}veness of improving the_heat shrlnkage. Further, the density of polypropylene subjected to no treatment such as extraction, is preferably 0.905 or higher, more preferably 0.910 or higher. If it is lower than such values, the effectiveness of improving the heat shrinkage is also insufficient.
Further, if the ratio of pentad having two different kinds of configurations (P2) exceeds 0.002, the effectiveness of improving the heat shrinkage is also insufficient.
The polypropylene used in the present invention has a higher melting point by 2C or more than those of conventional polypropylene and also a much higher ~Z0~260 degree of crystallizationA This is shown by measurement by means of e.g. DSC ~differential scanning caloximeter).
Further, the polypropylene has a higher arystallization rate from its molten state than those of conventional products; for example, the growth rate of its spherulites is higher and the number of its spherulite nuclei generated is larger. The fact that the polypropylene has a higher degree of crystallization and a much higher crystallization rate than those of conventional polypropylene is considered to be the cause of achievement of the improved heat shrinkage according to the present invention.
The polypropylene used in the present invention may, if necessary, contain an additive such as heat stabilizers,antioxidant, W absorber, antiblocking agent, coloring agent, etc. Further, when a nucleus-creating agent is added, a somewhat improvement in the heat-shrinkability is observed.
The polypropylene fibers referred to herein mean collectively products obtained by melt-spinning or extrud~ng the above-mentioned ~aly~rspylene, such as filaments, staple fibers, yarns of various shaped section, tows, flat yarns, stretched yarns, unstretched yarns, heat-treated yarns, secondarily processed products of the foregoing, etc. The above-mentioned flat yarns include those of 100 to 2000Ideniers used for fabrics _ 9 _ . .. . :
120426C) having a rectangular section, connected yarns of shaped section such as circular section or elliptical section having a plurality of single filaments connected in parallel (see Fig. 1), ribbed tapes (see Fig. 2), etc.
As for the spinning, stretching, heat treatment, etc. and apparatus therefore employed in the production of polypropylene fibers of the present invention, conventional ones may be applied. For example, flat yarns having an improved heat-shrinkability can be generally obtained by the following process: the melt flow rate (MFR) of polypropylene used in this case is suitably in the range of 1.0 to 7Ø If it is less than 1.0, extrusion property and stretchability are inferior, while it exceeds 7.0, the resulting flat yarn is liable to split in the direction of its stretching axis, resulting in reduction of loom-operating efficiency.
A polypropylene having a density of 0~905 or more, an isotactic pentad ratio of boiling n-heptane-insoluble portion tPo) of 0.960 or more and a ratio of pentad having two different kinds of configurations (P2), of 0.002 (0.2%) or less, is melted and kneaded by means of a conventional extruder, extruded from a T die, a circular die or the like, and cooled by means of e.g. chilled roll, dipping in a water tank, air cooling, etc. to make a film, which is then slit and stretched :lZ04Z60 under heatin~ by means of heated roll, hot air oven, infrared ray heater, steam, etc. The stretch ratio may be those employed conventionally. The resulting material is heated in a similar heating manner to that in the case of streching to effect relaxation annealing.
In this case, the percentage relaxation is preferably about 5 to 40%. The flat yarn thus obtained has a far less heat shrinkage than those of products obtained from conventional polypropylene resin in the same production manner as above. A remarkable difference is observed particularly in a high temperature region of 130C or higher, for example 130C to 155C. Thus, in order to obtain a heat-shrinkability to the same extent as in the case of flat yarn obtained by using conventional polypropylene, a less percentage relaxation is sufficient in the case of the present polypropylene i.e. an advantage of improving the productivility is obtained.
When a fabric is prepared by weaving the thus obtained flat yarns as warps and wefts and this fabric is used as a primary base of carpet, it is possible to obtain a carpet having a small shrinkage and a good quality even when heat treatment is carried out at a high temperature of 130C or higher, preferably 130C to 155C, more preferably 130C to 150~ in the production process of carpet.
~Z04Z~O
The present invention will be further described in details by way of Examples.
Example 1 and Comparative example 1 To a polypropylene having a melt flow rate of 3.8, a density of 0.910, an isotactic pentad ratio of boiling n-heptane-insoluble portion of 0.965 and a ratio of pentad having two different kinds of configurations of<O.OOZ were added 0.5% by weight of phenolic stabilizer and 0.1% by weight of calcium stearate, followed by pelletizing. The resulting pellets were melt-extruded by means of an extruder provided with a screw of 4Omm in diameter and a circular die, followed by cooling with a warm water at 40C to obtain a tubular film of 50 thick, which was then spit into tapes of 15mm wide, followed by stretching them in various ratios in the longitudinal direction, while heating by means of heated rolls having a surface temperature of 140C and subjecting to a 15~ relaxation heat treatment, while heating by means of two heated rolls having a surface temperature of 140DC and a hot air oven at 140C, to obtain flat yarns.
Their characteristic values are shown in Table 1 as Example 1. For comparison, to a polypropylene having a melt flow rate of 3.7, a density of 0.900 and an isotactic pentad ratio of boiling n-heptane-insoluble portion of 0.929 and a ratio of pentad having two different ~ .
lZ04260 kinds of configuration of 0.0~6 were added the above-mentioned additives, followed by pelletizing as mentionrd above. From th~ resulting pellets of conventional polypropylene resin were prepared flat yarns in the same manner as above. Their characteristic values are shown in Table 1 as Comparative example 1. Further the percentages heat shrinkage shown in Table 1 are also shown in Fig~ 1 wherein numeral 1 shows the case of Example 1 (stretch ratio: 6 times) and numeral 2 shows the case of Comparative example 1 (stretch ratio: 6 times).
Flat yarns of the present invention have a less percentage heat shrinkage than that of Comparative example. As apparent particularly from Fig. 1, a notable difference is observed at high temperature of 150C or higher. Nevertheless it is observed that their rigidity (Young's modulus) and tenacity are also high.
Examples 2-5 and Comparative examples 2-~
Example 1 was repeated except that only raw materials were varied. The extrusion properties, stretchability and percentage heat shrinkage in a stretch ratio of 6 times of the resulting products are shown in Table 2.
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~Z042160 As apparent from Table 2, any flat yarns prepared from a polypropylene having a density less than 0.905, a polypropylene having a PO less than 0.960 and a polypropylene having a P2 greater than 0.002 have a large heat shrinkability, whereas the flat ~arns prepared from polypropylene of the present invention have a small heat-shrinkability.
Example 6 and Comparative exmaple 5 To a polypropylene having a melt flow rate of 5.0, a density of 0.911, an isotactic pentad ratio of boiling n-heptane-insoluble portion of 0.960 and a ratio of pentad having two different kinds of configurations of<0.002 were pelletized. The resulting pellets were melt-extruded from an extruder of 4Omm~ through 150 nozzles of each a circular section and 0~5mm~
in diameter provided therein to obtain unstretched filaments of 15 deniers per filament which were then stretched in various ratios by means of a conventional stretching machine, followed by subjecting them to a 5% relaxation heat treatment while heating with a hot plate at 130C to obtain filaments of 3 to 6 deniers/filament. Their tenacity and heat shrinkage values were measured. The results are shown in Table
Fibers consisting of polypropylene resin have suitable tenacity characteristics imparted by orientation-crystallization during their spinning and stretching steps and have been used for practical uses, but they have such drawbacks that their tenacity is liable to be reduced and their shrinkage is liable to occur.
~Z14Z60 Thus in order to prevent shrinkage of their products with increase of time when they are preserved and used at room temperature, the fibers have been usually subjected to relaxation heat treatment at a temperature lower than the melting point of polypropylene after their stretching, to remove their internal strain formed when they are oriented during the spinning and stretching steps, i.e. their residual stress, which is a cause of the shrinkage and promote recrystallization to thereby stabilize the shrinkage. On the other hand, in order to make up the fibers into products, various secondary processings are required, and in the case of some products, the fibers are often subjected to various processes - exposed to an atmosphere at higher temperatures than room temperature; in particular, at higher temperatures than the heat treatment temperature, there occurs retrogradation of the orientation at the time of spinning and stretching whereby the shrinkage is rapidly increased.
Referring to flat yarns used as a primary backing of carpets, for example in the case of tufted carpets, polypropylene fibers are tufted on the backing and backed with a latex, followed by a latex-drying step; hence the fibers are exposed to a heated atmosphere at considerably high temperatures. Further, recently there is a tendency that the latex-drying step is carried lZI:)4Z60 out at higher temperatures and higher speeds to improve the productivity of the products. For example, when the fibers are allowed to stand at 130C for 15 minutes, if they have a heat-shrinkability endurable to the conditions, no problem has so far been raised, but a heat-shrinkability endurable to higher temperatures than such a temperature has recently come to be required.
In order to obtain a low heat-shrinkability under heating, i.e. the so-called low shrinkage, relaxation annealing may be generally applied after stretching, as described above, but the percentage relaxation has so far been generally 10 to 25%; if the percentage exceeds such values, a problem is raised that the productivity is reduced as much as the increase in the pexcentage relaxation.
Further, the percentage heat shrinkage of flat yarns is said to depend on the shrinkage of their non-crystallized portion caused by crystallization under heating, the recovery of the internal strain formed at the time of orientation by stretching and the retrogradation of the orientation. Thus, there has been employed a process of crystallizing the film prior to stretching as much as possible or subjecting the film after stretched to relaxation annealing to thereby effect removal of the internal strain and recrystallization.
12~4Z60 As for the process for advancing the crystallization of the film prior to stretching, as far as the aspect of processing is concerned, slow cooling is suitable for cooling the film just after extruded; hence air cooling manner is more advantageous than water cooling manner, and in the case of water cooling manner, cooling has been advantageiously carried out at a relatively high temperature of water. As far as the aspect of raw material is concerned, as for a process for enhancing the crystallization of the film or unstretched yarns, there has been employed a process of adding an organic neueleus-creating agent such as p-tertiary-butyl benzoic acid aluminum salt, dibenzylidene sorbitol, etc. to a conventional polypropylene resin . However, even though the above-mentioned processes are employed and further a relaxation annealing is added thereto, improvement in the heat-shrinkability at high temperatures, higher than 130C cannot be observed.
SUMMARY OF THE INVENTION
The obje~t of the present invention is to provide polypropylene fibers having a superior heat-shrinkability and excellent mechanical properties such as tenacity.
The present inventors have made strenuous studies on the above-mentioned problems, and have found that when a polypropylene having a density of 0.905 or more, 12~4260 an isotactic pentad ratio of boiling n-heptane-insoluble portion (Po) of 0~960 or more and a ratio of pentad having two different kinds of configurations (P2), of 0.002 or less is used as the raw material for polypropylene fibers, it is possible to improve the heat-shrinkability of the polypropylene fibers in the direction in which it is reduced to a large extent.
The present invention resides in Polyplopylene fibers having an improved heat-shrinkability and tenacity, which comprise a polypropylene resin having a density of 0.905 or more, an isotactic pentad ratio of boiling n-heptane-insoluble portion (Po) of 0.960 or more and a ratio of pentad having two different kinds of configurations tP2), of 0.002 (0.2%) or less.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows a laterally - cross-sectional view of an example of connected yarns.
Fig. 2 shows a laterally cross-sectional view of an example of ribbed tapes.
Fig. 3 shows a view of percentages heat shrinkage of flat yarns obtained in Example 1 and Comparative example 1, at various temperatures.
Fig. 4 shows a view of percentages heat shrinkage of stretched yarns obtained in Example 6 and Comparative example 5, at various temperatures.
1~4260 Fig. 5 shows a view illustrating the rel.ationship between the stretch ratio and tenaci.ty of stretched yarns o~tained in Example 6 and Comparative example 5.
DETAI:LED DESCRIPTION OF THE INVENTION
Polypropylene used in the present invention can be prepared according to the process described in the s.pecification of Japanese laid-open patent publication No. 58-104907, by polymeri~ing propylene in the presence of a catalyst prepared by reacting an organoaluminum compound or a reaction product of an organoaluminum compound with an electron donor, with TiCQ4., further reacting the resulting solid product ~II) with an electron donor and an electron acceptor, and then combining the resulting solid product ~III) with an organoaluminum compound and an aromatic carboxylic acid ester (V), the molar ratio of (V) to ~III) being 0.2 to 10Ø
Isotactic pentad.ratio referred to herein means an isotactic pentad ratio in terms of pentad units in the molecular chain of polypropylene, measured by using 13C-NMR (see A. Zambelli et al~ Macromolecules 6, 925 (1973)). In other words, the isotactic pentad ratio refers to a ratio of five continuously and isotactically connected propylene monomer.units in total propylene monomer units.
,i~ .
~Z042~0 The peak-assigning method in the above measurement by means of NMR was carried out based on Macromolecules 8,687 (1975)~ In addition, the measurement by means of NMR was carried out by using an apparaths of FT-5 NMR at 270 MHZ, and by improving th~ signal detectionlimit up to an isotactic pentad ratio of 0.001, by an integrating measurement of 27,000 times.
As to pentad, (1) an isotactic pentad is expressed by mmmm (00000) or (11111); (2) a pentad having one different kinds of configuration is expressed by either one of mmmr (00001) or (11110), mmrr (00010) or (11101), or mrrm (00100) or (11011); and (3) a pentad having two different kinds of configurations is expressed by mmrm (00011) or (11100), mrrr (00101) or (11010), mrmr (00110) or (11001), rrmr (01001~ or (10110), rrrr (01010) or (10101~ or rmmr (01110) or (10001), wherein m represents an isotactic dyad; r represents a syndiotactic dyad; and 0 and 1 each represents an individual monomer unit configuration along the polymer chain, and 0 represents a configuration while 1 represents a reverse configuration.
. 7 --lZ04Z60 The boiling n-heptane-insoluble portion of polypropylene used in the present invention refers to an extraction residue obtained by wholely dissolving 5g of polypropylene in 500ml of boiling xylene, pouring the solution in 5Q of methanol, recovering the resulting precipitate, drying it and extracting it with boiling n-heptane by means of a Soxhlet extractor for 6 hours. The density was determined by preparing a sample according to the press m~thod of JIS K 6758 and measuring it according to the underwater replacement method of JIS K 7112.
A polypropylene having an isotactic pentad ratio of boiling n-heptane-insoluble portion (P0) less than 0.~60 is insuffici~n~ i~ th~ effect}veness of improving the_heat shrlnkage. Further, the density of polypropylene subjected to no treatment such as extraction, is preferably 0.905 or higher, more preferably 0.910 or higher. If it is lower than such values, the effectiveness of improving the heat shrinkage is also insufficient.
Further, if the ratio of pentad having two different kinds of configurations (P2) exceeds 0.002, the effectiveness of improving the heat shrinkage is also insufficient.
The polypropylene used in the present invention has a higher melting point by 2C or more than those of conventional polypropylene and also a much higher ~Z0~260 degree of crystallizationA This is shown by measurement by means of e.g. DSC ~differential scanning caloximeter).
Further, the polypropylene has a higher arystallization rate from its molten state than those of conventional products; for example, the growth rate of its spherulites is higher and the number of its spherulite nuclei generated is larger. The fact that the polypropylene has a higher degree of crystallization and a much higher crystallization rate than those of conventional polypropylene is considered to be the cause of achievement of the improved heat shrinkage according to the present invention.
The polypropylene used in the present invention may, if necessary, contain an additive such as heat stabilizers,antioxidant, W absorber, antiblocking agent, coloring agent, etc. Further, when a nucleus-creating agent is added, a somewhat improvement in the heat-shrinkability is observed.
The polypropylene fibers referred to herein mean collectively products obtained by melt-spinning or extrud~ng the above-mentioned ~aly~rspylene, such as filaments, staple fibers, yarns of various shaped section, tows, flat yarns, stretched yarns, unstretched yarns, heat-treated yarns, secondarily processed products of the foregoing, etc. The above-mentioned flat yarns include those of 100 to 2000Ideniers used for fabrics _ 9 _ . .. . :
120426C) having a rectangular section, connected yarns of shaped section such as circular section or elliptical section having a plurality of single filaments connected in parallel (see Fig. 1), ribbed tapes (see Fig. 2), etc.
As for the spinning, stretching, heat treatment, etc. and apparatus therefore employed in the production of polypropylene fibers of the present invention, conventional ones may be applied. For example, flat yarns having an improved heat-shrinkability can be generally obtained by the following process: the melt flow rate (MFR) of polypropylene used in this case is suitably in the range of 1.0 to 7Ø If it is less than 1.0, extrusion property and stretchability are inferior, while it exceeds 7.0, the resulting flat yarn is liable to split in the direction of its stretching axis, resulting in reduction of loom-operating efficiency.
A polypropylene having a density of 0~905 or more, an isotactic pentad ratio of boiling n-heptane-insoluble portion tPo) of 0.960 or more and a ratio of pentad having two different kinds of configurations (P2), of 0.002 (0.2%) or less, is melted and kneaded by means of a conventional extruder, extruded from a T die, a circular die or the like, and cooled by means of e.g. chilled roll, dipping in a water tank, air cooling, etc. to make a film, which is then slit and stretched :lZ04Z60 under heatin~ by means of heated roll, hot air oven, infrared ray heater, steam, etc. The stretch ratio may be those employed conventionally. The resulting material is heated in a similar heating manner to that in the case of streching to effect relaxation annealing.
In this case, the percentage relaxation is preferably about 5 to 40%. The flat yarn thus obtained has a far less heat shrinkage than those of products obtained from conventional polypropylene resin in the same production manner as above. A remarkable difference is observed particularly in a high temperature region of 130C or higher, for example 130C to 155C. Thus, in order to obtain a heat-shrinkability to the same extent as in the case of flat yarn obtained by using conventional polypropylene, a less percentage relaxation is sufficient in the case of the present polypropylene i.e. an advantage of improving the productivility is obtained.
When a fabric is prepared by weaving the thus obtained flat yarns as warps and wefts and this fabric is used as a primary base of carpet, it is possible to obtain a carpet having a small shrinkage and a good quality even when heat treatment is carried out at a high temperature of 130C or higher, preferably 130C to 155C, more preferably 130C to 150~ in the production process of carpet.
~Z04Z~O
The present invention will be further described in details by way of Examples.
Example 1 and Comparative example 1 To a polypropylene having a melt flow rate of 3.8, a density of 0.910, an isotactic pentad ratio of boiling n-heptane-insoluble portion of 0.965 and a ratio of pentad having two different kinds of configurations of<O.OOZ were added 0.5% by weight of phenolic stabilizer and 0.1% by weight of calcium stearate, followed by pelletizing. The resulting pellets were melt-extruded by means of an extruder provided with a screw of 4Omm in diameter and a circular die, followed by cooling with a warm water at 40C to obtain a tubular film of 50 thick, which was then spit into tapes of 15mm wide, followed by stretching them in various ratios in the longitudinal direction, while heating by means of heated rolls having a surface temperature of 140C and subjecting to a 15~ relaxation heat treatment, while heating by means of two heated rolls having a surface temperature of 140DC and a hot air oven at 140C, to obtain flat yarns.
Their characteristic values are shown in Table 1 as Example 1. For comparison, to a polypropylene having a melt flow rate of 3.7, a density of 0.900 and an isotactic pentad ratio of boiling n-heptane-insoluble portion of 0.929 and a ratio of pentad having two different ~ .
lZ04260 kinds of configuration of 0.0~6 were added the above-mentioned additives, followed by pelletizing as mentionrd above. From th~ resulting pellets of conventional polypropylene resin were prepared flat yarns in the same manner as above. Their characteristic values are shown in Table 1 as Comparative example 1. Further the percentages heat shrinkage shown in Table 1 are also shown in Fig~ 1 wherein numeral 1 shows the case of Example 1 (stretch ratio: 6 times) and numeral 2 shows the case of Comparative example 1 (stretch ratio: 6 times).
Flat yarns of the present invention have a less percentage heat shrinkage than that of Comparative example. As apparent particularly from Fig. 1, a notable difference is observed at high temperature of 150C or higher. Nevertheless it is observed that their rigidity (Young's modulus) and tenacity are also high.
Examples 2-5 and Comparative examples 2-~
Example 1 was repeated except that only raw materials were varied. The extrusion properties, stretchability and percentage heat shrinkage in a stretch ratio of 6 times of the resulting products are shown in Table 2.
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~Z042160 As apparent from Table 2, any flat yarns prepared from a polypropylene having a density less than 0.905, a polypropylene having a PO less than 0.960 and a polypropylene having a P2 greater than 0.002 have a large heat shrinkability, whereas the flat ~arns prepared from polypropylene of the present invention have a small heat-shrinkability.
Example 6 and Comparative exmaple 5 To a polypropylene having a melt flow rate of 5.0, a density of 0.911, an isotactic pentad ratio of boiling n-heptane-insoluble portion of 0.960 and a ratio of pentad having two different kinds of configurations of<0.002 were pelletized. The resulting pellets were melt-extruded from an extruder of 4Omm~ through 150 nozzles of each a circular section and 0~5mm~
in diameter provided therein to obtain unstretched filaments of 15 deniers per filament which were then stretched in various ratios by means of a conventional stretching machine, followed by subjecting them to a 5% relaxation heat treatment while heating with a hot plate at 130C to obtain filaments of 3 to 6 deniers/filament. Their tenacity and heat shrinkage values were measured. The results are shown in Table
3.
At the same time, as an comparative example, to a polypropylene having a melt flow rate of 4.8, a density of 0.900, an isotactic pentad ratio of boiling n-heptane-insoluble portion of 0.935 and a ratio of pentad having two different kinds of configurations of 0.018 were pelletized as in the same manner as in Example 6. Using the resulting pellets, fibers were prepared in the same manner as in Example 6. The characteristic values of the fibers are shown in Table 3 as Comparative example 5. Further, the results of Table 3 are also shown in Fig. 4 and Fig. 5 wherein numeral 3 shows the case of Example 6 and numeral 4 shows that of Comparative example 5. ~stretch ratio: 6 times in both the cases~
Referring to Table 3 and Fig. 4 and Fig. 5, the fibers of the present invention have a less percentage heat shrinkage than that of Comparative example, and particularly from Fig. 4 it is observed that as the temperature becomes higher, a notable difference ~n t~heat-shrinkability is observed. Further, in Fig. 5, improvement in the tenacity is also observed.
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. _ ~Z~4260 Examples 7 and 8 and Comparative examples 6, 7 and 8 Example 6 was repeated except that only raw materials were varied. The resulting characteristics of percentage heat shrinkage and tenacity (stretch ratio: 6 times) are shown in Table 4.
As seen from Table 4, any fibers prepared from a polypropylene having a density less than 0.905, a polypropylene having a P0 less than 0.960 and a polypropylene having a P2 larger than 0.002 have a larger percentage heat shrinkage and also a less tenacity, whereas fibers prepared from polypropylene of the present invention have a less percentage heat shrinkage and an improved tenacity.
The polypropylene fibers according to the present invention have a much improved percentage heat shrinkage and also an improved tenacity, and in particular, as to the heat-shrinkability, since its effectiveness in a high temperature atmosphere is notable, if a drying step is required for carpet, etc., the fibers readily correspond to the tendency of rendering the drying temperature and speed at the step both higher;
hence an advantage is observed in the aspects of maintenance of product quality and high productivity.
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At the same time, as an comparative example, to a polypropylene having a melt flow rate of 4.8, a density of 0.900, an isotactic pentad ratio of boiling n-heptane-insoluble portion of 0.935 and a ratio of pentad having two different kinds of configurations of 0.018 were pelletized as in the same manner as in Example 6. Using the resulting pellets, fibers were prepared in the same manner as in Example 6. The characteristic values of the fibers are shown in Table 3 as Comparative example 5. Further, the results of Table 3 are also shown in Fig. 4 and Fig. 5 wherein numeral 3 shows the case of Example 6 and numeral 4 shows that of Comparative example 5. ~stretch ratio: 6 times in both the cases~
Referring to Table 3 and Fig. 4 and Fig. 5, the fibers of the present invention have a less percentage heat shrinkage than that of Comparative example, and particularly from Fig. 4 it is observed that as the temperature becomes higher, a notable difference ~n t~heat-shrinkability is observed. Further, in Fig. 5, improvement in the tenacity is also observed.
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. _ ~Z~4260 Examples 7 and 8 and Comparative examples 6, 7 and 8 Example 6 was repeated except that only raw materials were varied. The resulting characteristics of percentage heat shrinkage and tenacity (stretch ratio: 6 times) are shown in Table 4.
As seen from Table 4, any fibers prepared from a polypropylene having a density less than 0.905, a polypropylene having a P0 less than 0.960 and a polypropylene having a P2 larger than 0.002 have a larger percentage heat shrinkage and also a less tenacity, whereas fibers prepared from polypropylene of the present invention have a less percentage heat shrinkage and an improved tenacity.
The polypropylene fibers according to the present invention have a much improved percentage heat shrinkage and also an improved tenacity, and in particular, as to the heat-shrinkability, since its effectiveness in a high temperature atmosphere is notable, if a drying step is required for carpet, etc., the fibers readily correspond to the tendency of rendering the drying temperature and speed at the step both higher;
hence an advantage is observed in the aspects of maintenance of product quality and high productivity.
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Claims (4)
1. Polypropylene fibers having an improved heat-shrinkability and tenacity, which comprise a polypropylene resin having a density of 0.905 or more, an isotactic pentad ratio of boiling n-heptane-insoluble portion (P0) of 0.960 or more and a ratio of pentad having two different kinds of configurations (P2), of 0.002 (0.2%) or less.
2. Polypropylene fibers according to claim 1, which are subjected to a heat treatment at 130°C
or higher.
or higher.
3. Polypropylene fibers according to claim 1, wherein said polypropylene fibers are flat yarns and MFR of said polypropylene is in the range of 1.0 to 7Ø
4. Polypropylene fibers according to claim 3, which are subjected to a heat treatment at 130°C
or higher.
or higher.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57155752A JPS5947418A (en) | 1982-09-07 | 1982-09-07 | Flat yarn having improved heat shrinkability |
| JP57-155752 | 1982-09-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1204260A true CA1204260A (en) | 1986-05-13 |
Family
ID=15612637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000435884A Expired CA1204260A (en) | 1982-09-07 | 1983-09-01 | Polypropylene fibers having improved heat- shrinkability and tenacity |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4560734A (en) |
| JP (1) | JPS5947418A (en) |
| CA (1) | CA1204260A (en) |
| DE (1) | DE3332312A1 (en) |
| GB (1) | GB2127424B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE559298A (en) * | 1956-07-17 | |||
| US3054652A (en) * | 1957-08-28 | 1962-09-18 | Exxon Research Engineering Co | Isotactic polypropylene melt spinning process |
| US3152380A (en) * | 1961-05-05 | 1964-10-13 | Du Pont | Process for treating polypropylene fibers |
| US3413397A (en) * | 1961-08-17 | 1968-11-26 | Eastman Kodak Co | Process for stretching polypropylene filaments |
| US3705227A (en) * | 1971-01-13 | 1972-12-05 | Du Pont | Process and apparatus for quenching melt spun filaments |
| JPS5014864A (en) * | 1973-06-20 | 1975-02-17 | ||
| JPS53137268U (en) * | 1977-03-30 | 1978-10-30 | ||
| JPS54172069U (en) * | 1978-04-28 | 1979-12-05 | ||
| PH16274A (en) * | 1978-12-13 | 1983-08-26 | Sumitomo Chemical Co | Molded products of polypropylene |
| JPS58219207A (en) * | 1982-06-15 | 1983-12-20 | Chisso Corp | Polypropylene having high rigidity and melt viscoelasticity and preparation thereof |
-
1982
- 1982-09-07 JP JP57155752A patent/JPS5947418A/en active Granted
-
1983
- 1983-09-01 CA CA000435884A patent/CA1204260A/en not_active Expired
- 1983-09-06 GB GB08323842A patent/GB2127424B/en not_active Expired
- 1983-09-07 US US06/529,997 patent/US4560734A/en not_active Expired - Lifetime
- 1983-09-07 DE DE19833332312 patent/DE3332312A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB2127424A (en) | 1984-04-11 |
| US4560734A (en) | 1985-12-24 |
| JPS5947418A (en) | 1984-03-17 |
| DE3332312A1 (en) | 1984-03-08 |
| GB8323842D0 (en) | 1983-10-05 |
| JPH0372722B2 (en) | 1991-11-19 |
| DE3332312C2 (en) | 1987-11-05 |
| GB2127424B (en) | 1986-02-05 |
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