CA2248451C - Method for producing spun-bonded materials with improved tensile strength - Google Patents
Method for producing spun-bonded materials with improved tensile strength Download PDFInfo
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- CA2248451C CA2248451C CA002248451A CA2248451A CA2248451C CA 2248451 C CA2248451 C CA 2248451C CA 002248451 A CA002248451 A CA 002248451A CA 2248451 A CA2248451 A CA 2248451A CA 2248451 C CA2248451 C CA 2248451C
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Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
- D04H3/03—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
-
- 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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
Abstract
A spunbonded material having improved tensile strength is made by (1) continuously extruding a propylene homopolymer or random propylene/ethylene copolymer having a melt flow rate of about 3 to about 30 g/10 min at a temperature above 500°F through a spinneret to form discrete filaments, (2) drawing the filaments to molecularly orient the polymer filaments, and (3) depositing the filaments in a substantially random manner onto a carrier belt to form a web. The propylene polymer contains an additives package that includes an organic phosphite, a hindered phenol compound, calcium stearate, and, optionally, a hydrotalcite compound.
Description
Case 14008 This invention relates to a method for making spunbonded materials from propylene polymer materials.
Polypropylene resins are used to make nonwoven fabrics for applications such as diaper liners, medical gowns, and oil absorbents. One of the most important properties of these materials is their strength. For making conventional spunbonded materials, relatively high melt flow rate (MFR) resins (lower viscosity or lower molecular weight) are used at relatively low spinning temperatures, even though lower MFR
(higher viscosity or higher molecular weight) resins give greater fabric strength. If a low MFR
resin is employed, it cannot be processed at a normal spinning temperature because too many spin breaks occur. Spunbond fiber resins currently used have a MFR of about 40 and adequate spin continuity is maintained at a spinning temperature of about 210°C.
Various combinations of stabilizers have been used to prevent thermal degradation of polyolefins, as well as to increase resistance to degradation by light and to improve processability. Japanese published application 61-133251 discloses a heat resistant polyolefin resin molding composition containing a combination of a phenolic antioxidant, an organic phosphite, and hydrotalcite. U.5. 4, 611,024 discloses an injection molding grade resin that can also be used for making fibers and films. The resin contains an acetal clarifying agent and hydrotalcite. Optional ingredients include a phenolic antioxidant, an organic phosphite and a metal soap such as calcium stearate.
U.S. 4,965,301 discloses a stabilizer package for polyolefin fibers comprising (a) at least one hindered phenol, (b) at least one organic phosphite, (c) at least one hindered amine, (d) at least one metal salt of a long chain fatty acid, and (e) an alkali metal phosphate.
U.S. 5,246,777 discloses a fiber-forming polyolefin composition stabilized against heat, oxidation, light, and discoloration by combustion gases. The stabilizers include a hindered phenol, a hindered piperidine compound, and, optionally, an organic phosphorus compound antioxidant. Thus there is a need for a combination of additives that will provide spunbonded materials with increased tensile strength.
The process of this invention for making a spunbonded material comprises:
(a) continuously extruding a propylene polymer material selected from the group consisting of (i) a propylene homopolymer and (ii) a random copolymer of propylene and ethylene having an ethylene content of less than 10% by weight, having a melt flow rate of about 3 to about 30 g/10 min through a spinneret at a temperature greater than 500°F to form discrete filaments, (b) drawing the filaments to molecularly orient the polymer filaments, and (c) depositing the filaments in a substantially random manner onto a carrier belt to form a web, wherein the propylene polymer material contains additives consisting essentially of:
(i) about 250 parts to about 2500 parts of a pentaerythritol diphosphite, (ii) about 250 parts to about 2500 parts of a hindered phenol compound, (iii) about 100 parts to about 1 S00 parts of calcium stearate, and, optionally, (iv) about 5 to about 500 parts of a hydrotalcite compound, all parts being per million parts of the propylene polymer material.
The spunbonded material made by the process of this invention has improved tensile strength compared to conventional spunbonded materials while using a lower MFR
resin.
Fig. 1 is a plot of MD tensile strength (kg/osy) vs bonding temperature (°F) for materials made according to the process of this invention, compared with those made under conventional spunbonding conditions, and those made using the polymer and the spinning temperature of the process of this invention but having a less effective combination of additives. Osy = ounces per square yard.
Polypropylene resins are used to make nonwoven fabrics for applications such as diaper liners, medical gowns, and oil absorbents. One of the most important properties of these materials is their strength. For making conventional spunbonded materials, relatively high melt flow rate (MFR) resins (lower viscosity or lower molecular weight) are used at relatively low spinning temperatures, even though lower MFR
(higher viscosity or higher molecular weight) resins give greater fabric strength. If a low MFR
resin is employed, it cannot be processed at a normal spinning temperature because too many spin breaks occur. Spunbond fiber resins currently used have a MFR of about 40 and adequate spin continuity is maintained at a spinning temperature of about 210°C.
Various combinations of stabilizers have been used to prevent thermal degradation of polyolefins, as well as to increase resistance to degradation by light and to improve processability. Japanese published application 61-133251 discloses a heat resistant polyolefin resin molding composition containing a combination of a phenolic antioxidant, an organic phosphite, and hydrotalcite. U.5. 4, 611,024 discloses an injection molding grade resin that can also be used for making fibers and films. The resin contains an acetal clarifying agent and hydrotalcite. Optional ingredients include a phenolic antioxidant, an organic phosphite and a metal soap such as calcium stearate.
U.S. 4,965,301 discloses a stabilizer package for polyolefin fibers comprising (a) at least one hindered phenol, (b) at least one organic phosphite, (c) at least one hindered amine, (d) at least one metal salt of a long chain fatty acid, and (e) an alkali metal phosphate.
U.S. 5,246,777 discloses a fiber-forming polyolefin composition stabilized against heat, oxidation, light, and discoloration by combustion gases. The stabilizers include a hindered phenol, a hindered piperidine compound, and, optionally, an organic phosphorus compound antioxidant. Thus there is a need for a combination of additives that will provide spunbonded materials with increased tensile strength.
The process of this invention for making a spunbonded material comprises:
(a) continuously extruding a propylene polymer material selected from the group consisting of (i) a propylene homopolymer and (ii) a random copolymer of propylene and ethylene having an ethylene content of less than 10% by weight, having a melt flow rate of about 3 to about 30 g/10 min through a spinneret at a temperature greater than 500°F to form discrete filaments, (b) drawing the filaments to molecularly orient the polymer filaments, and (c) depositing the filaments in a substantially random manner onto a carrier belt to form a web, wherein the propylene polymer material contains additives consisting essentially of:
(i) about 250 parts to about 2500 parts of a pentaerythritol diphosphite, (ii) about 250 parts to about 2500 parts of a hindered phenol compound, (iii) about 100 parts to about 1 S00 parts of calcium stearate, and, optionally, (iv) about 5 to about 500 parts of a hydrotalcite compound, all parts being per million parts of the propylene polymer material.
The spunbonded material made by the process of this invention has improved tensile strength compared to conventional spunbonded materials while using a lower MFR
resin.
Fig. 1 is a plot of MD tensile strength (kg/osy) vs bonding temperature (°F) for materials made according to the process of this invention, compared with those made under conventional spunbonding conditions, and those made using the polymer and the spinning temperature of the process of this invention but having a less effective combination of additives. Osy = ounces per square yard.
Fig. 2 is a plot of CD tensile strength (kg/osy) vs bonding temperature (°F) for materials made according to the process of this invention, compared with those made under conventional spunbonding conditions, and those made using the polymer and the spinning temperature of the process of this invention but having a less ei~ective combination of additives.
The propylene homopolymer or random propylene/ethylene copolymer used in the process of this invention has a melt flow rate (1V>FR) of about 3 to about 30 g/ 10 min (ASTM D-1238, 2.16 kg at 230°C), preferably about 3 to about 25 g/10 min and most preferably about 3 to about 20 g/10 min. The copolymer preferably has an ethylene content of less than 10% ethylene.
Propylene polymer materials having a MFR within this range can be obtained by visbreaking a polymer having a lower MFR, i.e., subjecting the polymer to chain scission.
This process not only lowers the molecular weight and raises the melt flow rate of the polymers, but it also leads to a narrowing of the molecular weight distribution. Generally speaking, higher molecular weight leads to better physical properties but poorer processing properties. Conversely, lower molecular weight leads to poorer physical properties, but better processing properties. A low molecular weight polymer with narrow molecular weight distribution gives both good physical and processing properties in many fabricated articles. Therefore it is a common procedure to polymerize propylene, or propylene and ethylene, to a higher molecular weight than desired for the final application, and then to visbreak to the desired molecular weight.
In commercial practice visbreaking is generally achieved by the addition of a prodegradant to the polymer before pelletization. Alternatively, the polymer and the prodegradant can be mixed in the extruder while heating. A prodegradant is a substance that promotes chain scission when mixed with the polymer, which is then heated under extrusion conditions. The prodegradants used in current commercial practice are mainly alkyl hydroperoxides or dialkyl peroxides. These materials initiate a free radical chain reaction at elevated temperatures, resuhing in scission of the propylene polymer molecules.
In order to over<<orne the spinning problem inherent in Lhe use of a resin with a relatively !ow MFG higher spinning temperatures are used so that the melt viscosity of the .polymer at the spinnerer, die can be maintained at the same value as a higher M1FR resin at a normal spinning temperature. For example, the melt viscosity of a 10 MAR
resin at a melt temperature of 53~>°F is the same as that of a 38 MFR resin at a melt temperature of 410°p'. Therefore the spinnability of these two resins (10 and 38 MFR) will he the same at the respective spinning ternperatures_ In the process of this invention the propylene polymer is spun at a te~rtperature of greater than,.500°F
(260°C), preferably greater than S25°F (274°C).
Since higher than normal spinning temperatures are used during the process of this invention, an additive package is needed that provides strong stabilization against thermal degradation of the prolayl~ene polymer, which leads to poor fabric strength.
The additives package of this invention consists essentially of (a) a pentaerythritol diphosphite, (b) a hindered phenol compound, and (c) calcium stearate. Gptionally component (a) can be mixed with a hydrotalc:ite compound, e.g., it can be added as a product such as r3ltranox~
627A bis(2,4-di-t-but~~lph.enyl)pentaerythritol diphosphite, which contains 7%
DI3T-4A~
hydrotalcite compound having the forrnuia [Mg ~.SAIz(OT-~13CC3 . 3.51-T20].
Ultrattox~
627A stabilizer is commercially available from GE Specialty Chemicals. The hydtotalcite compound is not necessary for thermal stabilisation, but increases the hydrolytic stability of the pentaerythritol diphosphite, making it easier to handle.
The pentaeryth~itol diphosphite can be selected from compounds having the formula ~x ~t-~O-Py /C' /P-~OR~
~x CHsO
~' ~,~.cAa-.rn-o~.~-t-~,;~ a in which R' and R" are the same or different and are selected from C1_zo linear or branched alkyl, C5_zo cycloalkyl, C6_zo aryl, and Cz_zo alkoxyalkyl groups, and the halo-substituted derivatives thereof, as well as combinations such as alkaryl containing up to 20 carbon atoms per molecule. Preferably, R' and R" are the same and are alkaryl, most preferably alkylphenyl.
Specific examples of suitable pentaerythritol diphosphites include dimethylpentaerythritol diphosphite, diethylpentaerythritol diphosphite, didodecylpentaerythritol diphosphite, ditolylpentaerythritol diphosphite, distearyl pentaerythritol diphosphite, diphenyl pentaerythritol diphosphite, dibenzyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, and di-p-chlorophenyl pentaerythritol diphosphite. Other suitable organic phosphate compounds having this formula are disclosed in U.S. 4,025,486. Bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite is preferred.
The pentaerythritol diphosphite is present in an amount of about 250 to about 2500 parts per million parts of the propylene polymer material, preferably about 745 parts to about 1115 parts, and most preferably about 835 to about 1025 parts.
Hydrotalcite [Mg6Alz (OH) 16 C03 . 4H20] occurs naturally in small deposits in the former Soviet Union and also in Snarum, Norway. It can also be produced synthetically. The DHT-4A* product having the formula [Mg4_ SAlz (OH) 1303 . 3 . 5H20]
*Trade-mark i i w is a hydrotalcite-like compound that is available commercially from Kyowa Chemical Industry Co., Ltd. When present, the hydrotalcite compound is used in an amount of about 5 parts to about 500 parts per million parts of the propylene polymer material, preferably about 55 parts to about 85 parts, and most preferably about 60 to about 80 parts.
Suitable hindered phenol compounds include, for example, tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane; 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene; 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-trione; 3,9-bis[2-f3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy~-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and 5a 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,S~triazine-2,4,b(1H, 3H, 51~-i)-trione.
1,3,5-Trimethyl-2,4,6-Iris(3,S-di-t-butyl-4--hydrvxybenzyl)benzene is preferred.
The hindered phenol compound is present in an amount of about 250 parts to about 2500 parts, preferably about 800 pans to about 1200 parts, and most preferably about 900 to about 1104 parts per nxillion pats of the propylene polymer material_ The calcium steafate is present in an amount of about 100 pans to about 1500 parts, preferably about 2~~10 parts to about 360 parts, and most preferably about 270 to about 330 parts per millic5n parts ofthe propylene polymer material.
In order to obtaiat spunbanded materials with the high tensile strength of this invention it is necessary to use the combination of (1) a propylene polymer material having the specified melt flaw rate., (Z) the specified spinning temperature, and (3) .the specified combination of additive:..
The combination of additives can be incorporated into the propylene polymer material in any conventional manner, such as by dry blending the additives directly with polymer pellets or fluff, by means of, for example, tumble mixers and Henschel blenders, as is known in the an. Solutions or slurries of the additives can be sprayed onto or admixed with granular polymer. The additives can also be blended with molten polymer b means of for exam 1e a Banb ~ ' y , p , ury mixer, Brabender~'mixer, roll mill, or screw extruder.
A convenient method is to add the additives in dry form to granulated propylene polymer material, followed by extending to provide a peiletized product that subsequently can be used far forming fibers. Other additives such as, for example, fillers, extenders, plasticizers, coloring a~,ents, and other polymeric materials can be added to the propylene polymer material.
Spunbonded materials are prepared by continuously extruding the polymer through a spinneret to form discrete filaments. 'thereafter, the filaments are drawn either mechanically or pneumatically without breaking in order to molecularly orient the polymer filaments and achieve tenacity. Tine continuous filaments are then deposited in a substantially random manner onto a carrier belt to form a web.
~ T~rp~. -.,~. 6 xn Example 1 and Comparative Examples 1-3, the fibers and nonwoven materials were prepared an a 1 nveter wide lE~eicofi~pilot laboratory spunbond line under the conditions specified in "Table 1. Polymer B (Comparative Example 1), was spun under the current standard conditions used for making polypropylene spunbonded materials, i.e., a spinning temperature of 410°F {210°C). Polymers A, C1, and C2 were spun at 536°F
{2so°C).
The grab tensile strength of the spunbonded materials was measured using ASTM-L7 16$2 and ASTM-D 1 ~ 76.
Melt flow rates were measured according to ASTM b-1238 (2.16 kg, 230°C).
In this specification, all parts and percentages are by weight unless otherwise noted.
hxample 1 and Com,~,arative Examples I-3 Figures 1 and 2 show the dramatic increase in tensile strength in a spunbonded material made by the process of this invention (Polymer A) compared to those made from a standard spunbond resin spun under standard conditions (Polymer B, Comparative Example 1) and those; made using the spinning temperature and a polymer having the melt flow rate specified by the process of this invention, but without the specified combination of additives (Polymers C1 and C2, Comparative Examples 2 and 3). The spinning conditions are indicated in Table 1. In the figures, osy = ozJyd2.
In Table 1 and in Figures 1 and 2, Polymer A was a propylene homopolymer having a MFR of _10 p,/10 min.' The polymer was prepared by visbrealdng a propylene homopolymer havinl~ a ME'R of '1 g/10 min. The additives used in Example I
were a combination of (a) 100(> ppm EthanoX 330 1,3,5-trimethyl-2,4,6-tris(3,5.-di-tart-butyl-4-hydroxybenryl)benzene, commercially available from Aibemarle Corporation; (b) ppm UltranoXl627A bis(2,~4-di-t«butylphenyl)pentaerythritol diphosphite containing 7%
DT3T-4A~hydrotalcite compound, commercially available from GE Specialty Chemicals, and {c) 300 ppm calcium stearate.
Y0. c~
Polymer B was a Wdard spanbond resin having a MFR of 38 gJlO min, commercially available &am Montell 1'JSA inc., which was prepared by visbreaking a propylene homopolymer in Make form having a MfR of 0,4 g/10 min. The polymer contained 1000 ppm Irg:uMOx~076 oGtadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate antioxidant, commercially available from C133A Specialty Chernicsts Corporation, and 300 ppm calcium stearate.
Polymers Cl sad CZ were the same propylene hamopolymer as Polymer A, but contained a less effective combination of additives consisting of (a) 1000 ppm Irga~nox .
1076 antioxidant, and (i7) 300 ppm calcium stearate.
Table T
PolynecrMelt TbraughputCooling SuctionFyber Tentp. (g/holelmin)Air Temp.(rpm) Size (microns) Exam la A _., 536 0.35 50 2500 26 Com . ~ 410 0.35 50 2500 26 Ex. 1 Com . C1 536 0.35 50 2500 25 Ex. 2 Com . C2 53fi 0.35 SO 2200 26 Ex. 3 The data plotted in Figures. 1 and 2 show that when the 10 Ml'R polymer containing the combination of additives xpacefied in the process of this invention (Polymer A) was processed at a higher temperature to produce the same fiber sixe as that made I 5 from the standard spunbond resin (i'olymer $), it produced a fabric that had a significantly bugher grab tensile strength. The 10 MFR polymers containing a hindered phenol compound and calcium stearate (Polymers C 1 and C2) degraded more during spinning and produced fabrics with lower grab tensile strength than those made from the same MFR
polymer containing this morn effective combination of additives of this invention. For the 20 10 MFR polymers C 1 and C2, a finer fiber sine was obtained for Polymer C
1, which resulted in higher fabric strength comparod to Polymer C2. It should be noted that the suction pressure was lowered for Polymer Cx to pcloduce the same fiber size.
'~ Tcu,~a - .v~cr ~~
Samples containing different catabinations of additives in a propylene homopolymer (not visbroicen) having a MFR of 7.3 were prepared. The components of each sample were weighed and bag blended. A'/." compression screw with a 25:1 length:diameter ratio and a screw speed of 60 rpm were used for alI
extrusions_ The original sample was compounded at 245°C, with subsequent passes through the extruder at tha temperatures indicated in Table 2.
In Table 2 Ultrano~627A stabilizer is bis(2,4-dlt-butylphenyl)pentaerythritol diphosphite that contains 79~e DHT-~!A hydrotalcite compound having the formula [Mg'.
sAlz(OIi)~C03 . 3.5 Ha,O]. Ultranox~b26 is the same pentaerythritol diphosphite without the nHT. Eoth Uluanox. stabilizers are commercially available from GE
Specialty Chemicals, The sample having the lowest MFR at the highest temperature employed was most likely to produce spunbonded materials with the highest tensile suength. The results ars given in Table 2.
bet Sample 1 2 3 4 5 6 7 8 9 10 Polypropylene107 104 140 100 100 100 100 100 100 100 ~
IJltranox 0.1 0.1 0.1 62'1A~' Ethanox 330 0.1 0.1 0.1 0.1 0.1 0.1 Ca Stearate 0.03 0.030.03 4,03 I
Ultranox 626 0.09 0.09 0,1 1V~R (g/14 nun) Original 7,3 6.2 S.9 9.1 6.3 4.7 4.8 6.5 4.8 4.7 1'' Pass X260C11,57.3 7.0 19.47.2 5,~ 5.6 I1.15.6 5.5 I" Pass X290C20,29.0 8,2 29.28.9 6.1 6.0 15.26.5 6.6 ~1E'- g tr.~sc -~....~t A comparison of the data for samples 2 and 5, 6 and 7, and 9 and 10 shows that the hydrotalcite compound is not required for thermal stabilization.
Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosures. In this regard, while specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as described and claimed.
The propylene homopolymer or random propylene/ethylene copolymer used in the process of this invention has a melt flow rate (1V>FR) of about 3 to about 30 g/ 10 min (ASTM D-1238, 2.16 kg at 230°C), preferably about 3 to about 25 g/10 min and most preferably about 3 to about 20 g/10 min. The copolymer preferably has an ethylene content of less than 10% ethylene.
Propylene polymer materials having a MFR within this range can be obtained by visbreaking a polymer having a lower MFR, i.e., subjecting the polymer to chain scission.
This process not only lowers the molecular weight and raises the melt flow rate of the polymers, but it also leads to a narrowing of the molecular weight distribution. Generally speaking, higher molecular weight leads to better physical properties but poorer processing properties. Conversely, lower molecular weight leads to poorer physical properties, but better processing properties. A low molecular weight polymer with narrow molecular weight distribution gives both good physical and processing properties in many fabricated articles. Therefore it is a common procedure to polymerize propylene, or propylene and ethylene, to a higher molecular weight than desired for the final application, and then to visbreak to the desired molecular weight.
In commercial practice visbreaking is generally achieved by the addition of a prodegradant to the polymer before pelletization. Alternatively, the polymer and the prodegradant can be mixed in the extruder while heating. A prodegradant is a substance that promotes chain scission when mixed with the polymer, which is then heated under extrusion conditions. The prodegradants used in current commercial practice are mainly alkyl hydroperoxides or dialkyl peroxides. These materials initiate a free radical chain reaction at elevated temperatures, resuhing in scission of the propylene polymer molecules.
In order to over<<orne the spinning problem inherent in Lhe use of a resin with a relatively !ow MFG higher spinning temperatures are used so that the melt viscosity of the .polymer at the spinnerer, die can be maintained at the same value as a higher M1FR resin at a normal spinning temperature. For example, the melt viscosity of a 10 MAR
resin at a melt temperature of 53~>°F is the same as that of a 38 MFR resin at a melt temperature of 410°p'. Therefore the spinnability of these two resins (10 and 38 MFR) will he the same at the respective spinning ternperatures_ In the process of this invention the propylene polymer is spun at a te~rtperature of greater than,.500°F
(260°C), preferably greater than S25°F (274°C).
Since higher than normal spinning temperatures are used during the process of this invention, an additive package is needed that provides strong stabilization against thermal degradation of the prolayl~ene polymer, which leads to poor fabric strength.
The additives package of this invention consists essentially of (a) a pentaerythritol diphosphite, (b) a hindered phenol compound, and (c) calcium stearate. Gptionally component (a) can be mixed with a hydrotalc:ite compound, e.g., it can be added as a product such as r3ltranox~
627A bis(2,4-di-t-but~~lph.enyl)pentaerythritol diphosphite, which contains 7%
DI3T-4A~
hydrotalcite compound having the forrnuia [Mg ~.SAIz(OT-~13CC3 . 3.51-T20].
Ultrattox~
627A stabilizer is commercially available from GE Specialty Chemicals. The hydtotalcite compound is not necessary for thermal stabilisation, but increases the hydrolytic stability of the pentaerythritol diphosphite, making it easier to handle.
The pentaeryth~itol diphosphite can be selected from compounds having the formula ~x ~t-~O-Py /C' /P-~OR~
~x CHsO
~' ~,~.cAa-.rn-o~.~-t-~,;~ a in which R' and R" are the same or different and are selected from C1_zo linear or branched alkyl, C5_zo cycloalkyl, C6_zo aryl, and Cz_zo alkoxyalkyl groups, and the halo-substituted derivatives thereof, as well as combinations such as alkaryl containing up to 20 carbon atoms per molecule. Preferably, R' and R" are the same and are alkaryl, most preferably alkylphenyl.
Specific examples of suitable pentaerythritol diphosphites include dimethylpentaerythritol diphosphite, diethylpentaerythritol diphosphite, didodecylpentaerythritol diphosphite, ditolylpentaerythritol diphosphite, distearyl pentaerythritol diphosphite, diphenyl pentaerythritol diphosphite, dibenzyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, and di-p-chlorophenyl pentaerythritol diphosphite. Other suitable organic phosphate compounds having this formula are disclosed in U.S. 4,025,486. Bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite is preferred.
The pentaerythritol diphosphite is present in an amount of about 250 to about 2500 parts per million parts of the propylene polymer material, preferably about 745 parts to about 1115 parts, and most preferably about 835 to about 1025 parts.
Hydrotalcite [Mg6Alz (OH) 16 C03 . 4H20] occurs naturally in small deposits in the former Soviet Union and also in Snarum, Norway. It can also be produced synthetically. The DHT-4A* product having the formula [Mg4_ SAlz (OH) 1303 . 3 . 5H20]
*Trade-mark i i w is a hydrotalcite-like compound that is available commercially from Kyowa Chemical Industry Co., Ltd. When present, the hydrotalcite compound is used in an amount of about 5 parts to about 500 parts per million parts of the propylene polymer material, preferably about 55 parts to about 85 parts, and most preferably about 60 to about 80 parts.
Suitable hindered phenol compounds include, for example, tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane; 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene; 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-trione; 3,9-bis[2-f3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy~-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and 5a 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,S~triazine-2,4,b(1H, 3H, 51~-i)-trione.
1,3,5-Trimethyl-2,4,6-Iris(3,S-di-t-butyl-4--hydrvxybenzyl)benzene is preferred.
The hindered phenol compound is present in an amount of about 250 parts to about 2500 parts, preferably about 800 pans to about 1200 parts, and most preferably about 900 to about 1104 parts per nxillion pats of the propylene polymer material_ The calcium steafate is present in an amount of about 100 pans to about 1500 parts, preferably about 2~~10 parts to about 360 parts, and most preferably about 270 to about 330 parts per millic5n parts ofthe propylene polymer material.
In order to obtaiat spunbanded materials with the high tensile strength of this invention it is necessary to use the combination of (1) a propylene polymer material having the specified melt flaw rate., (Z) the specified spinning temperature, and (3) .the specified combination of additive:..
The combination of additives can be incorporated into the propylene polymer material in any conventional manner, such as by dry blending the additives directly with polymer pellets or fluff, by means of, for example, tumble mixers and Henschel blenders, as is known in the an. Solutions or slurries of the additives can be sprayed onto or admixed with granular polymer. The additives can also be blended with molten polymer b means of for exam 1e a Banb ~ ' y , p , ury mixer, Brabender~'mixer, roll mill, or screw extruder.
A convenient method is to add the additives in dry form to granulated propylene polymer material, followed by extending to provide a peiletized product that subsequently can be used far forming fibers. Other additives such as, for example, fillers, extenders, plasticizers, coloring a~,ents, and other polymeric materials can be added to the propylene polymer material.
Spunbonded materials are prepared by continuously extruding the polymer through a spinneret to form discrete filaments. 'thereafter, the filaments are drawn either mechanically or pneumatically without breaking in order to molecularly orient the polymer filaments and achieve tenacity. Tine continuous filaments are then deposited in a substantially random manner onto a carrier belt to form a web.
~ T~rp~. -.,~. 6 xn Example 1 and Comparative Examples 1-3, the fibers and nonwoven materials were prepared an a 1 nveter wide lE~eicofi~pilot laboratory spunbond line under the conditions specified in "Table 1. Polymer B (Comparative Example 1), was spun under the current standard conditions used for making polypropylene spunbonded materials, i.e., a spinning temperature of 410°F {210°C). Polymers A, C1, and C2 were spun at 536°F
{2so°C).
The grab tensile strength of the spunbonded materials was measured using ASTM-L7 16$2 and ASTM-D 1 ~ 76.
Melt flow rates were measured according to ASTM b-1238 (2.16 kg, 230°C).
In this specification, all parts and percentages are by weight unless otherwise noted.
hxample 1 and Com,~,arative Examples I-3 Figures 1 and 2 show the dramatic increase in tensile strength in a spunbonded material made by the process of this invention (Polymer A) compared to those made from a standard spunbond resin spun under standard conditions (Polymer B, Comparative Example 1) and those; made using the spinning temperature and a polymer having the melt flow rate specified by the process of this invention, but without the specified combination of additives (Polymers C1 and C2, Comparative Examples 2 and 3). The spinning conditions are indicated in Table 1. In the figures, osy = ozJyd2.
In Table 1 and in Figures 1 and 2, Polymer A was a propylene homopolymer having a MFR of _10 p,/10 min.' The polymer was prepared by visbrealdng a propylene homopolymer havinl~ a ME'R of '1 g/10 min. The additives used in Example I
were a combination of (a) 100(> ppm EthanoX 330 1,3,5-trimethyl-2,4,6-tris(3,5.-di-tart-butyl-4-hydroxybenryl)benzene, commercially available from Aibemarle Corporation; (b) ppm UltranoXl627A bis(2,~4-di-t«butylphenyl)pentaerythritol diphosphite containing 7%
DT3T-4A~hydrotalcite compound, commercially available from GE Specialty Chemicals, and {c) 300 ppm calcium stearate.
Y0. c~
Polymer B was a Wdard spanbond resin having a MFR of 38 gJlO min, commercially available &am Montell 1'JSA inc., which was prepared by visbreaking a propylene homopolymer in Make form having a MfR of 0,4 g/10 min. The polymer contained 1000 ppm Irg:uMOx~076 oGtadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate antioxidant, commercially available from C133A Specialty Chernicsts Corporation, and 300 ppm calcium stearate.
Polymers Cl sad CZ were the same propylene hamopolymer as Polymer A, but contained a less effective combination of additives consisting of (a) 1000 ppm Irga~nox .
1076 antioxidant, and (i7) 300 ppm calcium stearate.
Table T
PolynecrMelt TbraughputCooling SuctionFyber Tentp. (g/holelmin)Air Temp.(rpm) Size (microns) Exam la A _., 536 0.35 50 2500 26 Com . ~ 410 0.35 50 2500 26 Ex. 1 Com . C1 536 0.35 50 2500 25 Ex. 2 Com . C2 53fi 0.35 SO 2200 26 Ex. 3 The data plotted in Figures. 1 and 2 show that when the 10 Ml'R polymer containing the combination of additives xpacefied in the process of this invention (Polymer A) was processed at a higher temperature to produce the same fiber sixe as that made I 5 from the standard spunbond resin (i'olymer $), it produced a fabric that had a significantly bugher grab tensile strength. The 10 MFR polymers containing a hindered phenol compound and calcium stearate (Polymers C 1 and C2) degraded more during spinning and produced fabrics with lower grab tensile strength than those made from the same MFR
polymer containing this morn effective combination of additives of this invention. For the 20 10 MFR polymers C 1 and C2, a finer fiber sine was obtained for Polymer C
1, which resulted in higher fabric strength comparod to Polymer C2. It should be noted that the suction pressure was lowered for Polymer Cx to pcloduce the same fiber size.
'~ Tcu,~a - .v~cr ~~
Samples containing different catabinations of additives in a propylene homopolymer (not visbroicen) having a MFR of 7.3 were prepared. The components of each sample were weighed and bag blended. A'/." compression screw with a 25:1 length:diameter ratio and a screw speed of 60 rpm were used for alI
extrusions_ The original sample was compounded at 245°C, with subsequent passes through the extruder at tha temperatures indicated in Table 2.
In Table 2 Ultrano~627A stabilizer is bis(2,4-dlt-butylphenyl)pentaerythritol diphosphite that contains 79~e DHT-~!A hydrotalcite compound having the formula [Mg'.
sAlz(OIi)~C03 . 3.5 Ha,O]. Ultranox~b26 is the same pentaerythritol diphosphite without the nHT. Eoth Uluanox. stabilizers are commercially available from GE
Specialty Chemicals, The sample having the lowest MFR at the highest temperature employed was most likely to produce spunbonded materials with the highest tensile suength. The results ars given in Table 2.
bet Sample 1 2 3 4 5 6 7 8 9 10 Polypropylene107 104 140 100 100 100 100 100 100 100 ~
IJltranox 0.1 0.1 0.1 62'1A~' Ethanox 330 0.1 0.1 0.1 0.1 0.1 0.1 Ca Stearate 0.03 0.030.03 4,03 I
Ultranox 626 0.09 0.09 0,1 1V~R (g/14 nun) Original 7,3 6.2 S.9 9.1 6.3 4.7 4.8 6.5 4.8 4.7 1'' Pass X260C11,57.3 7.0 19.47.2 5,~ 5.6 I1.15.6 5.5 I" Pass X290C20,29.0 8,2 29.28.9 6.1 6.0 15.26.5 6.6 ~1E'- g tr.~sc -~....~t A comparison of the data for samples 2 and 5, 6 and 7, and 9 and 10 shows that the hydrotalcite compound is not required for thermal stabilization.
Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosures. In this regard, while specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as described and claimed.
Claims (3)
1. A process for making a spunbonded material comprising:
(a) continuously extruding a propylene polymer material selected from the group consisting of (i) a propylene homopolymer and (ii) a random copolymer of propylene and ethylene having an ethylene content of less than 10% by weight, having a melt flow rate of about 3 to about 30 g/10 min through a spinneret at atemperature greater than 500°F to form discrete filaments, (b) drawing the filaments to molecularly orient the polymer filaments, and (c) depositing the filaments in a substantially random manner onto a carrier belt to form a web, wherein the propylene polymer material contains additives consisting essentially of:
(i) about 250 parts to about 2500 parts of a pentaerythritol diphosphite, (ii) about 250 parts to about 2500 parts of a hindered phenol compound, (iii) about 100 parts to about 1500 parts of calcium stearate, and, optionally, (iv) about 5 to about 500 parts of a hydrotalcite compound, all parts being per million parts of the propylene polymer material.
(a) continuously extruding a propylene polymer material selected from the group consisting of (i) a propylene homopolymer and (ii) a random copolymer of propylene and ethylene having an ethylene content of less than 10% by weight, having a melt flow rate of about 3 to about 30 g/10 min through a spinneret at atemperature greater than 500°F to form discrete filaments, (b) drawing the filaments to molecularly orient the polymer filaments, and (c) depositing the filaments in a substantially random manner onto a carrier belt to form a web, wherein the propylene polymer material contains additives consisting essentially of:
(i) about 250 parts to about 2500 parts of a pentaerythritol diphosphite, (ii) about 250 parts to about 2500 parts of a hindered phenol compound, (iii) about 100 parts to about 1500 parts of calcium stearate, and, optionally, (iv) about 5 to about 500 parts of a hydrotalcite compound, all parts being per million parts of the propylene polymer material.
2. The process of claim 1, wherein the propylene polymer material has a melt flow rate of about 3 to about 20 g/10 min and is extruded at a temperature of greater than 525°F.
3. The process of claim 1, wherein (i) is present in an amount of about 745 to about 1145 part, (ii) is present in an amount of about 800 to about 1200 parts, (iii) is present in an amount of about 240 to about 360 parts, and (iv) is present in an amount of about 55 to about 85 parts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/940,719 US5858293A (en) | 1997-09-30 | 1997-09-30 | Method for producing spunbonded materials with improved tensile strength |
| US08/940,719 | 1997-09-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2248451A1 CA2248451A1 (en) | 1999-03-30 |
| CA2248451C true CA2248451C (en) | 2003-03-11 |
Family
ID=25475308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002248451A Expired - Fee Related CA2248451C (en) | 1997-09-30 | 1998-09-22 | Method for producing spun-bonded materials with improved tensile strength |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5858293A (en) |
| EP (1) | EP0905299B1 (en) |
| JP (1) | JPH11181665A (en) |
| KR (1) | KR19990030289A (en) |
| CN (1) | CN1096514C (en) |
| AT (1) | ATE237016T1 (en) |
| CA (1) | CA2248451C (en) |
| DE (1) | DE69813127T2 (en) |
| ES (1) | ES2193456T3 (en) |
| TW (1) | TW446776B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA03006783A (en) * | 2001-02-02 | 2004-10-15 | Polymer Group Inc | Process for producing continuous filament nonwoven fabric. |
| US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
| AU2003302033A1 (en) * | 2002-10-15 | 2004-06-15 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
| EP1983082B1 (en) * | 2006-02-06 | 2013-09-18 | Mitsui Chemicals, Inc. | Spunbonded nonwoven fabric |
| CN113186654B (en) * | 2021-04-26 | 2023-05-02 | 杭州科百特科技有限公司 | Polyester melt-blown non-woven fabric and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2075989B (en) * | 1980-05-13 | 1984-04-26 | Kyowa Chem Ind Co Ltd | Stabilized thermoplastic resin compositions |
| US4965301A (en) * | 1984-12-03 | 1990-10-23 | Phillips Petroleum Company | Stabilization of polyolefins |
| US4611024A (en) * | 1985-02-14 | 1986-09-09 | Phillips Petroleum Co. | Propylene polymer composition containing a hydrotalcite and an acetal of an alditol |
| JP2758031B2 (en) * | 1989-07-04 | 1998-05-25 | 協和化学工業株式会社 | Stabilizer composition for halogen-containing resin |
| US5246777A (en) * | 1990-04-25 | 1993-09-21 | Sumitomo Chemical Company, Limited | Fiber or film formed from a stabilized polyolefin composition |
| JP2965773B2 (en) * | 1990-12-05 | 1999-10-18 | 協和化学工業株式会社 | Heat stabilized halogen-containing resin composition having antistatic ability |
| US5362457A (en) * | 1992-08-13 | 1994-11-08 | Aluminum Company Of America | Direct synthesis of anion substituted hydrotalcite |
| US5352723A (en) * | 1992-09-15 | 1994-10-04 | Synthetic Products Company | Stabilized vinyl halide compositions containing hydrotalcites |
| US5849231A (en) * | 1993-03-29 | 1998-12-15 | General Electric Company | Melt extrusion process |
| CA2126013C (en) * | 1993-06-17 | 2000-08-15 | Leonardo Spagnoli | Spinning process for the preparation of high termoweldability polyolefin fibers |
| US5880186A (en) * | 1994-09-23 | 1999-03-09 | Ciba Specialty Chemicals Corporation | Stabilized filled polyolefins |
-
1997
- 1997-09-30 US US08/940,719 patent/US5858293A/en not_active Expired - Fee Related
-
1998
- 1998-09-22 CA CA002248451A patent/CA2248451C/en not_active Expired - Fee Related
- 1998-09-22 TW TW087115765A patent/TW446776B/en active
- 1998-09-26 DE DE69813127T patent/DE69813127T2/en not_active Expired - Fee Related
- 1998-09-26 AT AT98118276T patent/ATE237016T1/en not_active IP Right Cessation
- 1998-09-26 ES ES98118276T patent/ES2193456T3/en not_active Expired - Lifetime
- 1998-09-26 EP EP98118276A patent/EP0905299B1/en not_active Expired - Lifetime
- 1998-09-30 JP JP10277653A patent/JPH11181665A/en active Pending
- 1998-09-30 KR KR1019980040773A patent/KR19990030289A/en not_active Application Discontinuation
- 1998-09-30 CN CN98119443A patent/CN1096514C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1096514C (en) | 2002-12-18 |
| ES2193456T3 (en) | 2003-11-01 |
| JPH11181665A (en) | 1999-07-06 |
| DE69813127T2 (en) | 2003-12-04 |
| KR19990030289A (en) | 1999-04-26 |
| EP0905299B1 (en) | 2003-04-09 |
| ATE237016T1 (en) | 2003-04-15 |
| CN1213719A (en) | 1999-04-14 |
| TW446776B (en) | 2001-07-21 |
| US5858293A (en) | 1999-01-12 |
| EP0905299A2 (en) | 1999-03-31 |
| CA2248451A1 (en) | 1999-03-30 |
| EP0905299A3 (en) | 1999-09-22 |
| DE69813127D1 (en) | 2003-05-15 |
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