method for forming a poly (lactic acid) fiber, poly (lactic acid) fiber, and nonwoven weft

专利摘要:
METHOD FOR FORMING A POLY FIBER (LACTIC ACID) AND POLY FIBER (LACTIC ACID) The present invention provides a method for forming biodegradable fibers. The method includes combining poly (lactic acid) with a polyepoxide modifier to form a thermoplastic composition, extruding the thermoplastic composition through a mold, and therefore passing the extruded composition through a mold to form a fiber. Without claiming to be limited by theory, it is believed that the polyepoxide modifier reacts with the poly (lactic acid) and results in the branching of its polymeric main chain, thereby improving its melt strength and stability during spinning. fiber without significantly reducing the glass transition temperature. Reaction-induced branching can also increase molecular weight, which can lead to improved fiber ductility and the ability to improve dissipated energy when subjected to a stretching force. To minimize premature reaction, the poIi (lactic acid) and polyoxide modifier are first combined at a relatively low temperature. However, a relatively high shear rate can be employed during the combination to induce splitting of the poly (...) main chain.
公开号:BR112013003313B1
申请号:R112013003313-4
申请日:2011-07-06
公开日:2020-12-22
发明作者:Tyler J. Lark；Vasily A. Topolkaraev；Ryan J. Mceneany；Tom Eby
申请人:Kimberly-Clark Worldwide, Inc；
IPC主号:

专利说明:

HISTORY OF THE INVENTION
[001] Several attempts have been made to form nonwoven webs of biodegradable polymers. Although fibers prepared from biodegradable polymers are known, problems have been encountered with their use. For example, poly (lactic acid) ("PLA") is one of the most common sustainable and biodegradable polymers (renewable) used to form nonwoven fabrics. Unfortunately, PLA nonwoven webs generally have low bonding flexibility and high rigidity due to the high glass transition temperature and slow poly (lactic acid) crystallization rate. In turn, thermally bonded PLA nonwoven fabrics generally exhibit low elongations that are not acceptable in certain applications, such as an absorbent article. Likewise, although poly (lactic acid) can withstand high stretch ratios, it does require high levels of stretch energy to obtain the crystallization necessary to overcome thermal contraction. In response to these difficulties, plasticizers were used in an attempt to reduce the glass transition temperature and improve bonding and softness. A common plasticizer is poly (ethylene glycol). Unfortunately, poly (ethylene glycol) tends to separate from the poly (lactic acid) phase during aging, especially in an environment with high humidity and high temperature, which deteriorates the mechanical properties of the resulting fibers over time. The addition of plasticizers also causes other problems, such as degradation in melt spinning, and a reduction in melt strength and stretching ability.
[002] As such, a need currently exists for polylactic fibers that have good elongation properties to still remain strong. SUMMARY OF THE INVENTION
[003] According to an embodiment of the present invention, a method for forming a poly (lactic acid) fiber is described. The method comprises combining by melting a poly (lactic acid) with a polyepoxide modifier to form a thermoplastic composition, the melting combination occurring at a temperature above, the melting point of the poly (lactic acid) and below a temperature of about 230 ° C. The polyepoxide modifier has an average numerical molecular weight of about 7,500 to about 250,000 grams per head, with the amount of the polyepoxide modifier being about 0.01% by weight to about 10% by weight, based on in the weight of the poly (lactic acid). Accordingly, the thermoplastic composition is extruded at a temperature above about 230 ° C to facilitate the reaction of the polyepoxide modifier with the poly (lactic acid). The reacted composition is passed through a mold to form a fiber.
[004] According to another embodiment of the present invention, a poly (lactic acid) fiber is described which has an average diameter of about 5 to about 25 micrometers. The fiber comprises a thermoplastic composition formed by reacting poly (lactic acid) with a polyepoxide modifier, the polyepoxide modifier comprising a copolymer containing an epoxy modified monomeric (meth) acrylic component and an olefin monomeric component. The fiber has a glass transition temperature of about 55 ° C to about 65 ° C, and exhibits a peak elongation of about 50% or more and a toughness of about 7.35 to about 58.84 mN (about 0.75 to about 6 grams-strength) per denier.
[005] Other features and aspects of the present invention are discussed in more detail below. BRIEF DESCRIPTION OF THE DRAWINGS
[006] A complete and enabling description of the present invention, including its best mode, addressed to a person skilled in the art, is shown more particularly in the rest of the specification, which makes reference to the attached figures, in which: Figure i is a schematic illustration of a process that can be used in an embodiment of the present invention to form fibers; Figure 2 is a TEM photograph (60kV, 10,000X) of the polymer combination from Example 4, which contained 90% by weight of PLA 6201D (Natureworks®) and 10% by weight of poly (ethylene-co-acrylate) methacrylate methyl-co-glycidyl); Figure 3 is a TEM photograph (80kV, 10,000X) of the polymer combination from Example 49, which contained 98.23% by weight of PLA 6201D (Natureworks®), 2.52% by weight of PP3155 (Exxonmobil), and 0.75% by weight of Lotader® AX8900 (Arkema); Figure 4 is a TEM photograph (80kV, 10,000X) of the polymer combination of Example 50, which contained 89.5% by weight of PLA 6201D (Natureworks®), 10% by weight of PP3155 (Exxonmobil), and 0, 5% by weight of CESATM Extend 8478 (Clariant Corporation); and Figure 5 is a TEM photograph (60kV, 10,000X) of the polymer combination of Example 51, which contained 98.5% by weight of PLA 6201D (Natureworks®) and 1.5% by weight of Lotader® AX8900 (Arkema ).
[007] The repeated use of reference characters in this specification and in the drawings is intended to represent the same or similar characteristics or elements of the invention. DETAILED DESCRIPTION OF REPRESENTATIVE MODALITIES
[008] Reference will now be made in detail to the various modalities of the invention, one or more examples of which are presented below. Each Example is provided by way of explanation of the invention, and not by way of limitation of the invention. In reality, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. For example, the features illustrated or described as part of one modality, can be used in another modality to produce yet another modality. Thus, it is intended that the present invention covers such modifications and variations once they fall within the scope of the appended claims and their equivalents. Definitions
[009] As used here, the term "biodegradable" or "biodegradable polymer" generally refers to a material that degrades the action of naturally occurring microorganisms, such as bacteria, fungi, and algae; environmental warming; moisture; or other environmental factors. The biodegradability of a material can be determined using the ASTM Test Method 5338.92.
[0010] As used herein, the term "fibers" refers to elongated extrudates formed by passing a polymer through a forming hole such as a mold. Unless otherwise noted, the term "fibers" includes both staple fibers having a defined length and substantially continuous filaments. Substantially the filaments can, for example, be much longer than their diameter, such as a length-to-diameter ratio ("aspect ratio") greater than about 15,000 to 1, and in some cases, greater than about 50,000 to 1.
[0011] As used here, the term "monocomponent" refers to fibers formed from a polymer. This certainly does not exclude fibers to which additives have been added for color, antistatic properties, lubrication, hydrophilicity, liquid repellency, etc.
[0012] As used herein, the term "multicomponent" refers to fibers formed from at least two polymers (e.g. bicomponent fibers) that are extruded from separate extruders. The polymers are arranged in distinct zones substantially constantly positioned through the cross section of the fibers. The components can be arranged in any desired configuration, such as sheath-core, side-by-side, segmented pie, island in the sea, and so on. Various methods for forming multicomponent fibers are described in U.S. Patent Nos. 4,789,592 to Taniguchi et al. And U.S. Patent No. 5,336,552 to Strack et al., 5,108,820 to Kaneko, et al., 4,795,668 to Kruege, et al., 5,382,400 to Pike, and others, 5,336,552. by Strack, et al., and 6,200,669 by Marmon, et al., which are incorporated herein in their entirety by reference to this for all purposes. Multicomponent fibers having various irregular shapes can also be formed, as described in U.S. Patent Nos. 5,277,976 by Hogle, and others 5,162,074 by Hills. 5,466,410 from Hills. 5,069,970 by Largman, and others, and 5,057,368 by Largman, and others, which are incorporated herein in their entirety by reference to this for all purposes.
[0013] As used here, the term "nonwoven weave" refers to a weave having a structure of individual fibers that are randomly interwoven, not in an identifiable manner as in a knitted fabric. Nonwoven wefts include, for example, meltblown wefts, spunbond wefts, carded wefts, wet deposition wefts, airlaid wefts, accommodated wefts, hydraulically matted wefts, etc. The weight of the nonwoven fabric can generally vary, however, it is typically from about 5 grams per square meter ("g / m2") to 200 g / m2, in some embodiments from about 10 g / m2 to about 150 g / m2, and in some embodiments, from about 15 g / m2 to about 100 g / m2.
[0014] As used here, the term "meltblown" layer or weft generally refers to a non-woven weft that is formed by a process in which a molten thermoplastic material is extruded through a plurality of thin, usually circular, shaped capillaries as fibers fused in converging high-speed gas streams (eg, air) that attenuate the fibers of fused thermoplastic material to reduce their diameter, which can be to the diameter of microfiber. Therefore, the meltblown fibers are carried by the high-speed gas stream and are deposited on a collection surface to form a web of randomly dispersed meltblown fibers. Such a process is described, for example, in U.S. Patent Nos. 3,849,241 to Butin, and others; 4,307,143 to Meitner, and others; and 4,707,398 by Wisneski, et al., which are incorporated herein in their entirety by reference to this for all purposes. Meltblown fibers can be substantially continuous or discontinuous, and are generally adherent when deposited on a collection surface.
[0015] As used here, the term "spunbond" layer or weft generally refers to a nonwoven weft containing substantially continuous filaments of small diameter. The filaments are formed by extrusion of a thermoplastic material fused from a plurality of thin capillaries, usually circular from a spinner with the diameter of the extruded filaments, then being rapidly reduced, such as, for example, educational stretch and / or other well spunbond mechanisms. known. The production of spunbond wefts is described and illustrated, for example, in U.S. Patent Nos. 4,340,563 by Appel, et al., 3,692,618 by Dorschner, et al., 3,802,817 by Matsuki, et al., 3,338,992 by Kinney, 3,341,394 by Kinney, 3,502,763 by Hartman, 3,502,538 by Lew , 3,542,615 by Dobo, et al., And 5,382,400 by Pike, et al., Which are incorporated herein in their entirety by reference to this for all purposes.
[0016] Spunbond filaments are generally non-adherent when they are deposited on a collection surface. Spunbond filaments can sometimes be smaller in diameter than about 40 micrometers, and are generally between about 5 to about 20 micrometers. Test Methods Fused Flow Rate:
[0017] The molten flow rate ("MFR") is the weight of a polymer (in grams) forced through an extrusion rheometer orifice (0.209 cm (0.0825-inch) diameter) when subjected to a load of 2160 grams in 10 minutes, typically at 190 ° C or 230 ° C. Unless otherwise indicated, the melt flow rate is measured according to the ASTM D1239 Test Method with a Tinius Olsen Extrusion Plastomer. Thermal Properties:
[0018] The melting temperature and the glass transition temperature can be determined by differential scanning calorimetry (DSC). The differential scanning calorimetry can be a DSC Q100 differential scanning calorimetry, which has been equipped with a liquid nitrogen cooling accessory and a UNIVERSAL ANALYSIS 2.000 (version 4.6.6) analysis software program, both of which are available from TA Instruments Inc. of New Castle, Delaware. To avoid directly manipulating samples, tweezers or other tools are used. The samples are placed in an aluminum pan and weighed to an accuracy of 0.01 milligram on an analytical balance. A lid is crimped over the material sample in the pan.
[0019] Typically, the resin pellets are placed directly in the weighing pan, and the fibers are cut to accommodate placement in the weighing pan and covered by the lid.
[0020] Differential scanning calorimetry is calibrated using an Indian metal standard and a reference value correction is performed, as described in the operating manual for differential scanning calorimetry. A sample of the material is placed inside the differential scanning calorimetry test chamber for testing, and an empty pan is used as a reference. The entire test is performed with a 55 cubic centimeter per minute nitrogen (industrial grade) purge in the test chamber. For resin pellet samples, the heating and cooling program is a 2-cycle test that started with a chamber equilibrium at -30 ° C, followed by a first heating period and a heating rate of 10 ° C per minute at a temperature of 200 ° C, followed by equilibrating the sample at 200 ° C for 3 minutes, followed by a first cooling period at a cooling rate of 10 ° C per minute at a temperature of - 30 ° C, followed by equilibrate the sample at -30 ° C for 3 minutes, and then a second heating period at a heating rate of 10 ° C per minute at a temperature of 200 ° C. For fiber samples, the heating and cooling program is a 1-cycle test that started with a chamber equilibrium at 25 ° C, followed by a warm-up period at a heating rate of 10 ° C per minute at a temperature of 200 ° C, followed by equilibrating the sample at 200 ° C for 3 minutes, and then a cooling period at a cooling rate of 10 ° C per minute to a temperature of -30 ° C. The entire test is performed with a 55 cubic centimeter per minute nitrogen (industrial grade) purge in the purge chamber.
[0021] The results are evaluated using the analysis software program UNIVERSAL ANALYSIS 2.000, which identified and quantified the inflection glass transition temperature (Tg), the endothermic and exothermic peaks, and the areas under the peaks in the DSC plots. The glass transition temperature is identified as the region on the plotline where a distinct change in slope has occurred, and the melting temperature is determined using an automatic inflection calculation. Traction Properties:
[0022] Individual fiber specimens are shortened (for example, cut with scissors) to 38 millimeters in length, and placed separately on a black velvet cloth. 10 to 15 fiber specimens are collected in this way. The fiber specimens are then assembled in a substantially straight condition on a rectangular paper structure having an external dimension of 51 mm x 51 mm and an internal dimension of 25 mm x 25 mm. The ends of each fiber specimen are operatively attached to the structure by carefully attaching the ends of the fiber to the sides of the structure with adhesive tape. Each fiber specimen is then measured for its relatively short, transversal, external fiber dimension, using a conventional laboratory microscope, which has been properly calibrated and adjusted to 40X magnification. This transverse fiber dimension is recorded as the diameter of the individual fiber specimen. The structure helps to mount the ends of the sample fiber specimens in the upper and lower jaws at a constant rate of the extension type pull tester in a way to avoid excessive damage to the fiber specimens.
[0023] A constant rate of type of traction tester extension and an appropriate load cell are employed for verification. The load cell is chosen (for example, 10N) so that the test valve is included in 10-90% of the full scale load. The traction tester (i.e., MTS SYNERGY 200) and the load cell are obtained from MTS Systems Corporation of Eden Prairie, Michigan, USA. The fiber specimens in the assembly of the structure are then mounted between the jaws of the tensile tester such that the ends of the fibers are operatively maintained by the jaws of the tensile tester. Then, the sides of the paper structure that extend parallel to the length of the fiber are cut or otherwise separated so that the tensile tester applies the test force to the fibers only. The fibers are then subjected to a tensile test at a tensile rate and grapple speed of 30.48 cm (12 inches) per minute. The resulting data is analyzed using a TESTWORKS 4 software program from MTS Corporation with the following test configurations:

[0024] The toughness values are expressed in terms of gram-strength per denier. Peak elongation (% of tensile strength at break) is also measured. Moisture Content
[0025] The moisture content can be determined using an Arizona Instruments Computrac Vapor Pro moisture analyzer (Model No. 3100) substantially in accordance with ASTM D 7191 -05, which is incorporated here in its entirety by reference to this for all the purposes. The test temperature (5X2.1.2) can be 130 ° C, the sample size (§X2.1.1) can be 2 to 4 grams, and the flask purging time (§X2.1 .4) can be 30 seconds. In addition, the termination criteria (§X2.1.3) can be defined as a "prediction" mode, which means that the test is completed when the built-in programmed criteria (which mathematically calculates the endpoint moisture content) are satisfied . Detailed Description
[0026] In general, the present invention is concerned with a method for forming poly (lactic acid) fibers which includes combining the poly (lactic acid) with a polyepoxide modifier to form a thermoplastic composition, extruding the thermoplastic composition through a mold, and therefore passing the extruded composition through a mold to form a fiber. Without claiming to be limited to theory, it is believed that the polyepoxide modifier reacts with the poly (lactic acid) and results in the branching of its polymeric main chain, thereby improving its melt strength and stability during spinning of fibers without significantly reduce the glass transition temperature. Reaction-induced branching can also increase molecular weight, which can lead to improved fiber ductility and the ability to better dissipate energy when subjected to a stretching force. To minimize the premature reaction, the poly (lactic acid) and polyepoxide modifier are first combined together at a relatively low temperature. However, a relatively high shear rate can be employed during the combination to induce poly (lactic acid) backbone splitting, thereby making more hydroxyl and / or carboxyl groups available for subsequent reaction with the polyepoxide modifier. Once combined, the temperature (s) employed during the extrusion of the combined composition can be selected both to melt the composition and to initiate a reaction of the polypoxide modifier with hydroxyl and / or carboxyl groups of the poly (lactic acid). Through selective control over this method, the present inventors have found that the resulting fibers can exhibit good mechanical properties, both during and after melt spinning.
[0027] Various embodiments of the present invention will now be described in more detail. I. Thermoplastic Composition A. Poli (lactic acid)
[0028] Poly (lactic acid) can generally be derived from monomer units of any lactic acid isomer, such as levorotori-lactic acid ("L-lactic acid"), dextrorotatory-lactic acid ("D-lactic acid") , meso-lactic acid, or combinations thereof. Monomer units can also be formed from anhydrides of any lactic acid isomer, including L-lactide, D-lactide, meso-lactide, or combinations thereof. Cyclic dimers of such lactic acids and / or lactides can also be used. Any known polymerization method, such as polycondensation or ring opening polymerization, can be used to polymerize lactic acid. A small amount of a chain-extending agent (for example, a diisocyanate compound, an epoxy compound or an acid anhydride) can also be employed. The poly (lactic acid) can be a homopolymer or a copolymer, such as one that contains monomer units derived from L-lactic acid and monomer units derived from D-lactic acid. Although not required, the content rate of one of the monomer unit derived from L-lactic acid and the monomer unit derived from D-lactic acid is preferably about 85 mol% or more, in some embodiments about 90% mol or more, and in some embodiments, about 95 mol% or more. Multiple polylactic acids, each having a different relationship between the monomer unit derived from L-lactic acid and the monomer unit derived from D-lactic acid, can be combined in an arbitrary percentage. Of course, poly (lactic acid) can also be combined with other types of polymers (for example, polyolefins, polyesters, etc.) to provide a variety of different benefits, such as processing, fiber formation, etc.
[0029] In a particular modality, the poly (lactic acid) has the following general structure:

[0030] A specific example of a suitable poly (lactic acid) polymer that can be used in the present invention is commercially available from Biomer, Inc. of Krailling, Germany) under the name BIOMERTM L9000. Other suitable poly (lactic acid) polymers are commercially available from Natureworks LLC of Minnetonka, Minnesota (NATUREWORKS®) or Mitsui Chemical (LACEATM). Still other suitable polylactic acids can be described in U.S. Patent Nos. 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254; and 6,326,458, which are incorporated herein in their entirety by reference to this for all purposes.
[0031] poly (lactic acid) typically has a melting point of about 140 ° C to about 260 ° C, in some embodiments of about 150 ° C to about 250 ° C, and in some embodiments, of about from 160 ° C to about 220 ° C. Such polylactic acids are useful in that they biodegrade at a rapid rate. The glass transition temperature ("Tg") of the poly (lactic acid) can be relatively high, such as from about 40 ° C to about 80 ° C, in some embodiments from about 50 ° C to about 80 ° C, and in some embodiments, from about 55 ° C to about 65 ° C. As described in greater detail above, the melting temperature and glass transition temperature can be determined using differential scanning calorimetry ("DSC") according to ASTM D-3417.
[0032] poly (lactic acid) typically has an average numerical molecular weight ("Mn") ranging from about 40,000 to about 160,000 grams per mole, in some embodiments from about 50,000 to about 140,000 grams per mole, and in some modalities, from about 80,000 to about 120,000 grams per mol. Likewise, the polymer also typically has a weighted average molecular weight ('11 ,,.) Ranging from about 80,000 to about 200,000 grams per mol, in some embodiments from about 100,000 to about 180,000 grams per mol, and in some embodiments, from about 110,000 to about 160,000 grams per mol. The ratio of the weighted average molecular weight to the numerical average molecular weight ("Mw / Mr,"), that is, the "polydispersity index", is also relatively low. For example, the polydispersity index typically ranges from about 1.0 to about 3.0, in some embodiments from about 1.1 to about 2.0, and in some embodiments, from about 1.2 to about 1.8. The numerical average weight and molecular weights can be determined by methods known to those skilled in the art.
[0033] poly (lactic acid) can also have an evident viscosity of about 50 to about 600 Pascal.second (Pa. $), In some embodiments from about 100 to about 500 Pa.s, and in some embodiments , from about 200 to about 400 Pa.s, when determined at a temperature of 190 ° C and a shear rate of 1,000 sec-1. The melt flow rate of the poly (lactic acid) (on a dry basis) can also vary from about 0.1 to about 40 grams per 10 minutes, in some embodiments from about 0.5 to about 20 grams per 10 minutes, and in some embodiments, from about 5 to about 15 grams for 10 minutes, determined at a load of 2,160 grams and at 190 ° C. B. Poliepoxide Modifier
[0034] The polyepoxide modifier is a polymer that contains, on average, at least two oxirane rings per molecule. Without claiming to be limited to theory, it is believed that polyepoxide molecules can induce the chain extension of the poly (lactic acid) under certain conditions, thereby improving their melt strength without significantly reducing the glass transition temperature. Chain extension can occur through a variety of different reaction series. For example, the modifier can allow a nucleophilic ring opening reaction through the carboxyl terminal group of the poly (lactic acid) (esterification) or through a hydroxyl group (etherification). Oxazoline side reactions can likewise occur to form stearide fractions. Through such reactions, the molecular weight of the poly (lactic acid) can be increased to compensate for the degradation generally observed during melt processing. While it is desirable to induce a reaction with poly (lactic acid) as described above, the present inventors have found that the majority of a reaction can lead to crosslinking between polylactic backbones. If such crosslinking is allowed to proceed to a significant extent, the resulting polymer combination can become brittle and difficult to stretch into fibers with the desired elongation and strength properties. In this regard, the present inventors have found that the polyepoxide modifiers, which have relatively low epoxy functionality, are particularly effective, which can be quantified by their "epoxy equivalent weight". The epoxy equivalent weight reflects the nuance of a nup rnr11-4m in a C1P module or a pndwi frame. P can be calculated by dividing the average numerical molecular weight of the modifier by the number of epoxy groups in the molecule. The polyepoxide modifier of the present invention typically has an average numerical molecular weight of about 7,500 to about 250,000 grams per mole, in some embodiments from about 15,000 to about 150,000 grams per mole, and in some embodiments, from about 20,000 to 100,000 grams per mole, with a polydispersity index typically ranging from 2.5 to 7. The polyepoxide modifier can contain less than 50, in some embodiments from 5 to 45, and in some embodiments, from 5 to 40 epoxy groups . In turn, the epoxy equivalent weight may be less than about 15,000 grams per mole, in some embodiments from about 200 to about 10,000 grams per mole, and in some embodiments, from about 500 to about 7,000 grams per mol.
[0035] The polyepoxide can be a linear or branched homopolymer or copolymer, (for example, random, graft, block, etc.) containing terminal epoxy groups, skeletal oxirane units, and / or pendant epoxy groups. The monomers used to form such polyepoxides can vary. In a particular embodiment, for example, the polyepoxide modifier contains at least one epoxy-functional acrylic (meth) acrylic component. As used herein, the term "(meth) acrylic" includes acrylic and methacrylic monomers, as well as salts or esters thereof, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meth) acrylic monomers may include, but are not limited to, those containing 1,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate, and glycidyl itoconate.
[0036] Poliepoxide typically has a relatively high molecular weight, as indicated above, so that it can not only result in chain extension of the poly (lactic acid), but also helps to achieve the desired combination morphology, as will be described in further details below. The melt flow rate resulting from the polymer is thus typically within a range of about 10 to about 200 grams for 10 minutes, in some embodiments of about 40 to about 150 grams for 10 minutes, and in some embodiments, from about 60 to about 120 grams for 10 minutes, determined at a load of 260 grams and at a temperature of 190 ° C.
[0037] If desired, additional monomers can also be used in the polyepoxide to help obtain the desired molecular weight. Such monomers may vary and include, for example, ester monomers, (meth) acrylic monomers, olefin monomers, amide monomers, etc. In a particular embodiment, for example, the polyepoxide modifier includes at least one linear or branched α-olefin monomer, such as those having 2 to 20 carbon atoms and preferably 2 to 8 carbon atoms. Specific examples include ethylene, propylene, 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. The particularly desired α-olefin comonomers are ethylene and propylene.
[0038] Another suitable monomer may include an (meth) acrylic monomer that is epoxy-non-functional. Examples of such (meth) acrylic monomers can include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, acrylate of t-butyl, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethyl butyl acrylate, 2-ethylexyl acrylate, n-octyl acrylate, n-decyl acrylate, acrylate methylcyclohexyl, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, i-propyl methacrylate, methacrylate n-amyl, nhexyl methacrylate, i-amyl methacrylate, s-butyl-methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, crotyl methacrylate methacrylate cyclopentyl, 2-ethoxyethyl methacrylate, i methacrylate ground, etc., as well as combinations thereof.
[0039] In a particularly desirable embodiment of the present invention, the polyepoxide modifier is a terpolymer formed of an epoxy-functional (meth) acrylic component, a-olefin monomeric component, and a non-functional epoxy monomer (meth) acrylic component. . For example, the polyepoxide modifier can be poly (ethylene-co-methylacrylatoco-glycidyl methacrylate), which has the following structure:
where x, y, and z are 1 or more.
[0040] The functional epoxy monomer can be formed into a polymer using a variety of known techniques. For example, a monomer containing polar functional groups can be grafted onto a polymeric backbone to form a graft copolymer. Such grafting techniques are well known in the art and described, for example, in U.S. Patent No. 5,179,164, which is incorporated herein in its entirety by reference to this for all purposes. In other embodiments, a monomer containing epoxy functional groups can be copolymerized with a monomer to form a block or random copolymer using known free radical polymerization techniques, such as high pressure reactions, Ziegler-Natta catalyst reaction systems, single site catalyst reaction system (eg metallocene), etc.
[0041] The relative part of the monomeric component (s) can be selected to achieve a balance between epoxy reactivity and molten flow rate. More particularly, high levels of epoxy monomer can result in good reactivity with poly (lactic acid), however, excess of one content can reduce the melt flow rate as the polypoxide modifier adversely impacts melt resistance. of the polymer combination. Thus, in most embodiments, the epoxy-functional acrylic monomer (s) (meth) constitutes from about 1% by weight to about 25% by weight, in some embodiments from about 2% by weight to about 20% % by weight, and in some embodiments, from about 4% by weight to about 15% by weight of the copolymer. The α-olefin monomer (s) can likewise comprise from about 55% by weight to about 95% by weight, in some embodiments from about 60% by weight to about 90% by weight, and in some embodiments, from about 65% by weight to about 85% by weight of the copolymer. When used, other monomeric components (for example, epoxy-non-functional (meth) acrylic monomers) may comprise from about 5% by weight to about 35% by weight, in some embodiments from about 8% by weight to about 30% by weight, and in some embodiments, from about 10% by weight to about 25% by weight of the copolymer. A specific example of a suitable polyepoxide modifier that can be used in the present invention is commercially available from Arkema under the name Lotader® AX8950. Lotader® AX8950 has a melt flow rate of 70 to 100 g / 10 min and has a glycidyl methacrylate monomer content of 7% by weight to 11% by weight, a content of methyl acrylate monomer of 13% in weight at 17% by weight, and an ethylene monomer content of 72% by weight at 80% by weight.
[0042] In addition to controlling the type and relative content of the monomers used to form the polyepoxide modifier, the percentage of total weight can also be controlled to obtain the desired benefits. For example, if the level of modification is very low, the desired increase in melt strength and mechanical properties may not be achieved. The present inventors have also found, however, that if the level of modification is very high, the stretching of the fiber may be restricted due to strong molecular interactions (for example, crosslinking) and physical network formation by epoxy functional groups. Thus, the polyepoxide modifier is typically employed in an amount of about 0.01% by weight to about 10% by weight, in some embodiments from about 0.05% by weight to about 5% by weight, in some embodiments from about 0.1% by weight to about 1.5% by weight, and in some embodiments, from about 0.2% by weight to about 0.8% by weight, based on weight of the poly (lactic acid) used in the composition.
[0043] Depending on what other components are employing, the concentration of the polyepoxide modifier in the total thermoplastic composition may be equal to or less than the ranges noted above. In certain embodiments, for example, the polyepoxide modifier constitutes from about 0.01% by weight to about 10% by weight, in some embodiments from about 0.05% by weight to about 5% by weight some embodiments from about 0.1% by weight to about 1.5% by weight, and in some embodiments, from about 0.2% by weight to about 0.8% by weight, based on the total weight composition. Likewise, poly (lactic acid) typically constitutes about 70% by weight or more, in some embodiments, from about 80% by weight to about 99% by weight, and in some embodiments, from about 85% by weight. weight about 95% by weight of the composition. C. Stiffening Additive
[0044] Although not necessarily required, the thermoplastic composition of the present invention can also contain one or more polymeric stiffening additives or more polymeric stiffening additives to improve the melt strength and wiring stability of the composition during fiber formation. A benefit of the present invention is that when such additives are employed, the hydrophobic part of the polyepoxide modifier (e.g., olefin monomer) can also interact with the stiffening additive to form a substantially homogeneous compatibilized nanodispersion of the stiffening additive in the mold. poly (lactic acid). Such uniform distribution helps to obtain good mechanical properties of the resulting fibers.
[0045] Due to its polymeric nature, the stiffening additive has a relatively high molecular weight that can help to improve the melt resistance and stability of the thermoplastic composition. It is typically desired that the polymeric stiffening additive is generally immiscible with poly (lactic acid). In this way, the stiffening additive can become dispersed as discrete phase domains in a continuous phase of the poly (lactic acid). The discrete domains are able to absorb energy arising from the tension transmitted during the stretching of the composition during the stretching of the fiber, which increases the strength and total stiffness of the resulting fibers. While polymers are generally immiscible, the stiffening additive can, however, be selected to have a solubility parameter that is relatively similar to that of poly (lactic acid). This generally improves the interfacial adhesion and physical interaction of the discrete and continuous phase thresholds, and thereby reduces the likelihood of the composition fracturing when stretching. In this respect, the ratio of the solubility parameter for poly (lactic acid) to that of the stiffening additive is typically from about 0.5 to about 1.5, and in some embodiments, from about 0.8 to about 1.2. For example, the polymeric stiffening additive may have a solubility parameter of about 15 to about 30 MJoules1 / 2 / m3 / 2, and in some embodiments, from about 18 to about 22 Woules1 / 2im3'2, while the same time that the poly (lactic acid) can have a solubility parameter of about 20.5 MJoules1 / 2 / m3 / 2. The term "solubility parameter" as used here refers to the "Hildebrand Solubility Parameter", which is the square root of the cohesive energy density and calculated according to the following equation:
where: A Hy = heat of vaporization R = Constant of Ideal Gas T = Temperatira Vm = Molecular Volume
[0046] Hildebrand solubility parameters for polymeric mites are also available from Solibility Handbook of Plastics, by Wyeych (2004), which is incorporated here by reference.
[0047] The polymeric stiffening additive can also be selected to have a certain melt flow rate (or viscosity) to ensure that the discrete domains can be properly maintained. For example, if the melt flow rate of the stiffening additive is too high, it will tend to flow and disperse uncontrollably through the continuous phase.
[0048] This results in lamellar or plate-like domains that are difficult to maintain and also likely to prematurely fracture during stretching of the fiber. Conversely, if the melt flow rate of the stiffening additive is too low, it will tend to form lumps together and form very large elliptical domains, which are difficult to disperse during combination. This can cause non-uniform distribution of the stiffening additive throughout the entire continuous phase. In this respect, the ratio of the melt flow rate of the stiffening additive to the melt flow rate of the poly (lactic acid) is typically from about 0.2 to about 8, in some embodiments from about 0.5 to about from 6, and in some embodiments, from about 1 to about 5. The polymeric stiffening additive, for example, has a melt flow rate of about 0.1 to about 250 grams for 10 minutes, in some embodiments from about 0.5 to about 200 grams for 10 minutes, and in some embodiments, from about 5 to about 150 grams for 10 minutes, determined at a load of 2,160 grams and at 190 ° C.
[0049] In addition to the properties noted above, the mechanical characteristics of the polymeric stiffening additive can also be selected to obtain the desired increase in stiffening of the fiber. For example, the stiffening additive may have a relatively low Young's modulus of elasticity compared to poly (lactic acid). For example, the ratio of the elastic modulus of poly (lactic acid) to that of the stiffening additive is typically about 1 to about 250, in some embodiments from about 2 to about 100, and in some embodiments, from about 2 to about 50. The modulus of elasticity of the stiffening additive can, for example, vary from about 2 to about 500 Megapascals (MPa), in some embodiments from about 5 to about 300 MPa, and in some modalities, from about 10 to about 200 MPa. In contrast, the modulus of elasticity of poly (lactic acid) is typically from about 800 MPa to about 2,000 MPa. The polymeric stiffening additive can also exhibit a peak elongation (i.e., the percentage of elongation of the polymer at its peak load) greater than that of poly (lactic acid). For example, the polymeric stiffening additive of the present invention may exhibit a peak elongation of about 50% or more, in some embodiments about 100% or more, in some embodiments of about 100% to about 2,000%, and in some modalities, from about 250% to about 1,500%.
[0050] While a wide variety of polymeric additives can be employed, which have the properties identified above, particularly suitable Examples of such polymers may include, for example, polyolefins (for example, polyethylene, polypropylene, polybutylene, etc.); polytetrafluoroethylenes; polyesters (for example, recycled polyesters, polyethylene terephthalate, etc.); polyvinyl acetates (for example, poly (ethylene vinyl acetate), polyvinyl chloride acetate, etc.); polyvinyl alcohols (for example, polyvinyl alcohol, poly (ethylene) vinyl alcohol, etc .; polyvinyl butyrals; acrylic resins (for example, polyacrylate, polymethylacrylate, polymethylmethacrylate, etc.); polyamides (for example, nylon); polyvinyl; polyvinylidene chlorides; polystyrenes; polyurethanes, etc. Suitable polyolefins may, for example, include ethylene polymers (for example, low density polyethylene ("LDPE"), high density polyethylene ("HDPE"), polyethylene of linear low density ("LLDPE"), etc.), propylene homopolymers (for example, syndiotactic, atactic, isotactic, etc.), propylene copolymers, and so on.
[0051] In a particular embodiment, the polymer is a propylene polymer, such as homopolypropylene or a propylene copolymer. The propylene polymer can, for example, be formed from a substantially isotactic polypropylene homopolymer or a copolymer containing equal to or less than about 10% by weight of another monomer, that is, at least about 90% by weight of propylene. Such homopolymers can have a melting point of about 160 ° C to about 170 ° C.
[0052] In yet another embodiment, the polyolefin can be a copolymer of ethylene or propylene with another a-olefin, such as a C3-C20 a-olefin or C3-C12 a-olefin. Specific examples of suitable α-olefins include 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1- pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. Particularly the desired alpha olefin comonomers are 1butene, 1-hexene and 1-octene. The ethylene or propylene content of such copolymers can be from about 60 mol% to about 99 mol%, in some embodiments from about 80 mol% to about 98.5 mol%, and in some embodiments from about 87 mol% to about 97.5 mol%. The α-olefin content can likewise vary from about 1 mol% to about 40 mol%, in some embodiments from about 1.5 mol% to about 15 mol%, and in some embodiments , from about 2.5 mol% to about 13 mol%.
Exemplary olefin copolymers for use in the present invention include ethylene-based copolymers available under the name EXACTrm from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are available under the designation ENGAGETM, AFFINITY'M, DOWLEXTM (LLDPE) and ATTANE'm (ULDPE) from Dow Chemical Company of Midland, Michigan. Other suitable ethylene polymers are described in U.S. Patent Nos. 4,937,299 by Ewen and others, 5,218,071 by Tsutsui and others, 5,272,236 by Lai, and others, and 5,278,272 by Lai, and others, which are incorporated herein in their entirety by reference to this for all purposes . Suitable propylene copolymers are also commercially available under the VISTAMAXXTM designations of ExxonMobil Chemical Co. of Houston, Texas; FINATM (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMERTm available from Mitsui Petrochemical Industries; and VERSIFYTM available from Dow Chemical Co. of Midland, Michigan, USA. Other Examples of suitable propylene polymers are described in US Patent No. 6,500,563 to Datta, and others, 5,539,056 to Yang, and others, and 5,596,052 to Resconi, and others, which are incorporated herein in their entirety by reference to this for all purposes.
Any of a variety of known techniques can generally be employed to form the olefin copolymers. For example, olefin polymers can be formed using a free radical or a coordinating catalyst (for example, Ziegler-Natta). Preferably, the olefin polymer is formed from a single site coordination catalyst, such as a metallocene catalyst. Such a catalyst system produces ethylene copolymers in which the comonomer is randomly distributed in a molecular chain and uniformly distributed across different molecular weight fractions. Metallocene-catalyzed polyolefins are described, for example, in U.S. Patent Nos. 5,571,619 by McAlpin et al; 5,322,728 to Davis et al; 5,472,775 to Obiieski et al; 5,272,236 to Lai et al; and 6,090,325 by Wheat, et al., which are incorporated herein in their entirety by reference to this for all purposes. Examples of metallocene catalysts include bis (n-butylacyclopentadienyl) titanium dichloride, bis (n-butylacyclopentadienyl) zirconium dichloride, scandium bis (cyclopentadienyl) chloride, bis (indenyl) zirconium dichloride, titanium dichloride , bis (methylcyclopentadienyl) dichloride zirconium, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafnocene dichloride, isopropyl dichloride (-1-flourenyl cyclopentadieni1, -1-flourenyl), zirconium, molybdenum dichloride, rhodocene dichloride, molybdenum dichloride zirconocene chloride hydride, zirconocene dichloride, and so on. Polymers made using metallocene catalysts typically have a narrow molecular weight range. For example, metallocene-catalyzed polymers may have polydispersity numbers (Mw / Mn) below 4, controlled short chain branch distribution, and controlled isotacticity.
[0055] When used, the amount of the stiffening additive is typically about 1% by weight to about 25% by weight, in some embodiments from about 2% by weight to about 20% by weight, and in some embodiments, from about 5% by weight to about 15% by weight of the thermoplastic composition. D. Other Components
[0056] A beneficial aspect of the present invention is that good mechanical properties (for example, elongation) can be provided without the need for conventional plasticizers, such as alkylene glycols (for example, polyethylene glycols, such as those made available by Dow Chemical under the name Carbowaxn "), alkane diols, and alkylene oxides that have one or more hydroxyl groups that attack the poly (lactic acid) ester bonds and result in hydrolytic degradation. Other examples of such plasticizers are described in US Patent No. 2010 / 0048082 by Topolkaraev, et al., Which are incorporated herein in their entirety by reference to this for all purposes.The thermoplastic composition can be substantially free of such plasticizers, however, it should be understood that plasticizers can be used in certain embodiments When used, however, plasticizers are typically present in an amount of less than q u about 10% by weight, in some embodiments from about 0.1% by weight to about 5% by weight, and in some embodiments, from about 0.2% by weight to about 2% by weight of thermoplastic composition.
[0057] Certainly, other ingredients can be used for a variety of different reasons. For example, materials that can be used include, without limitation, catalysts, pigments, antioxidants, stabilizers, surfactants, waxes, solid solvent flow promoters, compatibilizers, nucleating agents (eg titanium dioxide, calcium carbonate, etc. .), particulates, and other materials added to enhance the processability of the thermoplastic composition. When used, it is normally desired that the amounts of these additional ingredients are minimized to ensure optimal compatibility and economy. Thus, for example, it is usually desired that such ingredients constitute less than about 10% by weight, in some embodiments less than about 8% by weight, and in some embodiments, less than about 5% by weight of the thermoplastic composition.
[0058] It should also be understood that other components can be included in the thermoplastic composition. Such a component that can be used is an additional biodegradable polyester, including aliphatic polyesters, such as polycaprolactase, polyesteramides, modified polyethylene terephthalate, poly (lactic acid) (PLA) and its copolymers, terpolymers based on poly (lactic acid), acid polyglycolic, polyalkylene carbonates (for example, polyethylene carbonate), poly-3-hydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxybutyrate-co-4-hydroxybirate, poly-3- copolymer hydroxybutyrate-co-3-hydroxyvalerate (PHBV), poly-3-hydroxybutyrate-co-3-hydroxyexanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxidecanoate, poly-3 -hydroxybutyrate-co-3-hydroxyoctadecanoate, and aliphatic polymers based on succinate (eg, polybutylene succinate, polybutylene succinate adipate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (for example, polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene adipate isophthalate, polybutylene adipate isophthalate, etc.), and so on. II. Combination
[0059] Pure poly (lactic acid) will generally absorb water from the environment such that it has a moisture content of about 500 to 600 parts per million ("ppm"), or even higher, based on the dry weight of the poly (acid starting). The moisture content can be determined in a variety of ways as is known in the art, such as according to ASTM D 7191- 05, as described above.
[0060] Because the presence of water during melting processing can hydrolytically degrade the poly (lactic acid) and reduce its molecular weight, it is sometimes desired to dry the poly (lactic acid) before the combination. In most embodiments, for example, poly (lactic acid) is desired to have a moisture content of about 200 parts per million ("ppm") or less, in some embodiments from about 1 to about 100 ppm, and in some embodiments, from about 2 to about 80 ppm before combining with the polyepoxide modifier. The drying of the poly (lactic acid) can occur, for example, at a temperature of about 50 ° C to about 100 ° C, and in some embodiments, from about 70 ° C to about 80 ° C.
[0061] The combination of the components of the thermoplastic composition can be performed using any of a variety of known techniques. In one embodiment, for example, the raw materials (for example, poly (lactic acid) and polyepoxide modifier) can be supplied separately or in combination. For example, raw materials can first be combined dry together to form an essentially homogeneous dry combination. The raw materials can likewise be supplied either simultaneously or in sequence to a melt processing device that dispersively combines the materials. Batch and / or continuous fusion processing techniques can be employed. For example, a mixer / kneader, mixed from Banbury, continuous mixer from Farrel, single-screw extruder, twin-screw extruder, roller mill, etc., can be used for the process of combining and casting the materials. Particularly suitable foundry processing devices can be a cogiratory extruder, twin-screw extruder (eg, ZSK-30 extruder available from Werner & Pfleiderer Corporation of Ramsey, New Jersey, USA or a Thermo PrismrM USALAB 16 extruder available from Thermo Electron Corp., Stone, England). Such extruders can include ventilation and supply holes and provide dispersive and dibutrative combinations. For example, the poly (lactic acid) and polyepoxide modifier can be fed into the same or different feed holes of the twin-screw extruder combined by melting to form a substantially homogeneous molten combination. If desired, additives (for example, stiffening additive) can also be injected into the molten polymer and / or separately fed into the extruder at a different point along its length. Alternatively, the additives can be pre-combined with the poly (lactic acid) and / or the polyepoxide modifier.
[0062] Regardless of the particular processing technique chosen, the raw materials are mixed with high shear / pressure and low heating to ensure sufficient dispersion without causing the polyepoxide modifier to undergo a substantial reaction with the poly (lactic acid) prematurely. For example, the combination typically occurs at a temperature above the melting point of the poly (lactic acid), but below the temperature used to initiate the reaction of the polyepoxide modifier to a significant extent (for example, about 230 ° C ), such as from about 170 ° C to about 230 ° C, in some embodiments from about 180 ° C to about 220 ° C, and in some embodiments, from about 185 ° C to about 215 ° C . Likewise, the shear rate evident during melt processing can range from about 100 seconds-1 to about 10,000 seconds-1, in some embodiments from about 200 seconds-1 to about 5000 seconds-1, and in some modalities, from about 500 seconds-1 to about 1200 seconds-1. The evident shear rate is 4Q / nR3, where Q is the volumetric flow rate ("m3 / s") of the polymer melt and R is the radius ("m") of the capillary (for example, extruder mold ) through which the molten polymer flows. Certainly, other variables, such as the residence time during melting processing, which is inversely proportional to the productivity rate, can also be controlled to obtain the desired degree of homogeneity.
[0063] Due to the selective control over the polyepoxide (for example, activity, molecular weight, etc.) and the particular conditions of combination by fusion, the present inventors found that a morphology can be formed which enhances the reactivity with the poly ( lactic acid). More particularly, the resulting morphology can have a plurality of discrete phase domains of the polyepoxide modifier distributed throughout the continuous poly (lactic acid) mold. The domain can have a variety of different shapes, such as elliptical, spherical, cylindrical, etc. Regardless of the shape, however, the size of an individual domain, after combining, is small to provide an increased surface area for subsequent reaction with the poly (lactic acid). For example, the size of a domain (for example, length) typically ranges from about 10 to about 1000 nanometers, in some modalities, from about 20 to about 800 nanometers, in some modalities from about 40 to about 600 nanometers, and in some modalities from about 50 to about 400 nanometers. The optional stiffening additive can also form discrete domains in the poly (lactic acid) mold. When formed, such domains are typically larger than the polyepoxide domains. For example, the stiffening additive domains can have a dimension (e.g., length) of about 0.5 gm at about 30 pm, and in some embodiments from about 1 pm to about 10 pm. Of course, it should also be understood that the domains can be formed by a combination of the polyepoxide, stiffening additive, and / or other components of the combination. III. Reaction Technique
[0064] The reaction of the combined polyepoxide and poly (lactic acid) modifier is conducted at the same time as the initial polymers are in the molten phase ("melt processing") to minimize the need for additional solvents and / or removal processes solvent. More specifically, the combination can be supplied to an extruder (for example, single spindle) that includes a rotatingly mounted screw and received in a drum (for example, cylindrical drum), which can be heated. The combination is moved downstream from a feed end to a discharge end by forces exerted by the rotation of the screw. Such screw extruders are typically divided into three sections along the length of the screw. The first section is a feed section where the solid material is introduced to the screw. The second section is a smelting section where most solid smelting takes place. In this section, the screw usually has a tapered diameter to enhance the casting of the polymer. The third section is the combining section, which releases the molten material in a constant amount for extrusion. The screw configuration is not particularly critical to the present invention and can contain any number and / or orientation of wires and channels as is known in the art.
[0065] Before leaving the extruder through a mold, the molten plastic can also travel through one or more screens ("packaging with screen") in the drum that are optionally reinforced by a shredder plate. In addition to removing contaminants and unfused solids, assembling the shredder plate from the screened packaging can help create back pressure in the drum to enhance the uniformity of the melting and polymer combination. The amount of intake pressure can be controlled by varying the configuration of the packaging with mesh (the number of mesh, size of the mesh hole, etc.). The screen packaging may include, for example, 2 to 15 screens, in some modalities from 3 to 10 screens, and in some modalities, from 4 to 8 screens. When multiple screens are employed, the upstream screens are usually one size to collect only large particles while the subsequent downstream screens are one size to collect smaller and smaller particles. Although fabrics of various sizes can be employed, it is typically desired that the package employs at least one fabric having openings of a relatively small size to create a sufficiently high back pressure in the drum. For example, the screen may contain openings having an average width (or diameter) of about 100 micrometers or less, in some embodiments about 75 micrometers or less, and in some embodiments, from about 1 to about 50 micrometers. Preferably, the package employs multiple screens (for example, 3 or more) having openings of this size.
[0066] The speed of the screw can also be selected to obtain the desired residence time, shear rate, melt processing temperature, etc. For example, the speed of the screw can vary from about 50 to about 200 revolutions per minute ("rpm"), in some modalities from about 70 to about 150 rpm, and in some modalities, from about 80 to about 120 rpm. This can result in a temperature that is higher than that normally used to extrude the poly (lactic acid) and high enough to initiate the reaction of the polyepoxide modifier, such as above about 230 ° C. For example, the extruder can employ one or multiple zones, at least one of which operates at a temperature from about 230 ° C to about 350 ° C, in some embodiments from about 235 ° C to about 300 ° C, and in some embodiments, from about 240 ° C to about 280 ° C.
[0067] The melting shear rate, and in turn the degree to which the reaction is initiated, can also be increased through the use of one or more distributive and / or dispersive combination elements in the extruder combination section. Distributive mixers suitable for single-screw extruders may include, for example, Saxon, Dulmage, Cavity Transfer mixers, etc. Likewise, suitable dispersive mixers may include Blister rings, Leroy / Maddock, CRD mixers, etc. As is well known in the art, the combination can also be improved by using pins on the drum that create a fold and reorientation of the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers, and Vortex Intermeshing Pin mixers ( VIP).
[0068] Regardless of the particular elements selected, the use of one or more combination elements can create intensive melting shear rates that help initiate the desired reaction. Typically, the shear rate evident during fusion processing can range from about 100 seconds-1 to about 10,000 seconds-1, in some embodiments from about 200 seconds-1 to about 5000 seconds-1, and in some modalities, from about 500 seconds-1 to about 1,200 seconds-1. Certainly, other variables, such as the residence time during melting processing, which is inversely proportional to the productivity rate, can also be controlled to obtain the desired degree of reaction.
[0069] In addition to controlling the shear conditions, the present inventors have also found that the moisture content of the precursor combination can also be controlled to help achieve the desired degree of reaction. Without claiming to be limited to theory, it is believed that water can act as a catalyst for the reaction of polyepoxide and poly (lactic acid). However, excess moisture content can lead to the degradation of poly (lactic acid) and a reduction in its molecular weight. In this regard, the present inventors have found that the moisture content of the precursor combination can be controlled to a moisture content of about 00 to about 500 ppm, in some embodiments from about 25 to about 400 ppm, and in some modalities, from about 150 to about 300 ppm. Such moisture contents can be obtained by drying, such as at a temperature of about 40 ° C to about 80 ° C, and in some embodiments, from about 50 ° C to about 70 ° C.
[0070] In differentiating from the initial polymer in certain properties, poly (lactic acid) can, however, maintain other properties of the initial polymer. For example, because the thermoplastic composition used to form the fibers generally does not contain a plasticizer, the glass transition temperature (Tg) of the reacted composition is typically the same as the poly (lactic acid) glass transition temperature. That is, the reacted thermoplastic composition can have a Tg of about 50 ° C to about 80 ° C, and in some embodiments, from about 55 ° C to about 65 ° C. The melting point of the thermoplastic composition can also vary from about 150 ° C to about 250 ° C, and in some embodiments, from about 160 ° C to about 220 ° C. IV. Fiber Formation
[0071] The fibers formed from the reacted thermoplastic composition can generally have any desired configuration, including monocomponent and multicomponent (for example, sheath-core configuration, side-by-side configuration, segmented pie configuration, island configuration in the ocean, and so on) against). In some embodiments, the fibers may contain one or more additional polymers as a component (eg, bicomponent) or constituent (eg, biconstituent) for additional strength enhancement and other mechanical properties. For example, the thermoplastic composition can form a sheath component of a fiber and two-component sheath / core, while an additional polymer can form the core component, or vice versa. The additional polymer can be a thermoplastic polymer that is not generally considered to be biodegradable, such as polyolefins, for example, polyethylene, polypropylene, polybutylene, and so on; polytetrafluoroethylene; polyesters, for example, polyethylene terephthalate, and so on; polyvinyl acetate; polyvinyl chloride acetate; polyvinyl butyral; acrylic resins, for example, polyacrylate, polymethylacrylate, polymethylmethacrylate, and so on; polyamides, for example, nylon; polyvinyl chloride; polyvinylidene chloride; polystyrene; polyvinyl alcohol; and polyurethanes. Most desirably, however, the additional polymer is biodegradable, such as aliphatic polyesters, such as polyesteramides, modified polyethylene terephthalate, polyglycolic acid, polyalkylene carbonates (such as polyethylene carbonate), polyhydroxyalkanoates (PHA), polyhydroxybutyrates (PHB), polyhydroxyvalerates (PHV), polyhydroxybutyrate hydroxyvalerate (PHBV) copolymers, and polycaprolactone, and succinate-based aliphatic polymers (for example, polybutylene succinate, polybutylene succinate adipate, and polyethylene succinate); aromatic polyesters; or other aromatic aliphatic copolyesters.
[0072] Any of a variety of processes can be used to form fibers according to the present invention. For example, the thermoplastic composition described above can be extruded through a spinner, passed through thermal shock (quenching), and stretched in the vertical passage of a fiber stretching unit. The reaction of the polyepoxide and poly (lactic acid) modifier can occur during this process, or it can occur before introduction into the fiber forming line. Once formed, the fibers can then be cut to form textile fibers having an average fiber length in the range of about 3 to about 80 millimeters, in some embodiments from about 4 to about 65 millimeters, and in some embodiments, from about 5 to about 50 millimeters. The textile fibers can then be incorporated into a nonwoven weave as is known in the art, such as continuous carded weaves, continuous weaves through the air, etc. The fibers can also be deposited on a foraminous surface to form a nonwoven web.
[0073] Referring now to Figure 1, for example, a modality of a method for forming fibers is shown in greater detail. In this particular embodiment, the pre-mixed thermoplastic composition is extruded at a relatively high temperature to induce the reaction between the modifier's epoxy functional group and the poly (lactic acid), as well as to initiate fiber formation. For example, the poly (lactic acid) / polyepoxide modifier combination is fed into an extruder 12 from a hopper 14. The combination can be supplied to the hopper 14 using any conventional technique. As described in detail above, extruder 12 is heated to a temperature sufficient to extrude the melted polymer and initiate the reaction between the polypoxide modifier and the poly (lactic acid). The extruded composition is then passed through a polymer tube 16 to a spinner 8. For example, the spinner 18 can include a box containing a spinner pack having a plurality of plates stacked on top of each other and having a pattern of openings arranged to create flow paths to direct the polymer components. The spinneret 18 also has openings arranged in one or more rows. The openings form a downward extrusion curtain of filaments when the polymers are extruded into them. Process 10 also employs an extinguishing insufflator 20 positioned adjacent to the fiber curtain extending from the spinner 18. The air from the extinguishing air insufflator 20 extinguishes the fibers extending from the spinner 18. The extinguishing air can be directed from a side of the fiber curtain as shown in Figure 1 or both sides of the fiber curtain.
[0074] After extinction, the fibers are extended in the vertical passage of a fiber stretch unit 22. The fiber stretch unit or vacuum cleaner for use in melt spinning polymers is well known in the art. The fiber drawing unit suitable for use in the process of the present invention includes a linear fiber vacuum cleaner of the type shown in U.S. Patent Nos. 3,802,817 and 3,423,255, which are incorporated herein in their entirety by reference to this for all material purposes. The fiber drawing unit 22 generally includes an elongated vertical passageway through which the fibers are drawn by suctioning air that enters the sides of the passageway and flows downwardly through the passageway. A heater or insufflator 24 provides suction of air to the fiber stretch unit 22. The suction air pulls the fibers and the ambient air through the fiber stretch unit 22. The gas flow causes the fibers to stretch or attenuate what increases the molecular orientation or crystallinity of the polymers forming the fibers. The fibers are deposited through the outlet opening of the fiber drawing unit 22 and onto a roller (godet roll) 42. Due to the high strength of the fibers of the present invention, high stretch ratios can be employed in the present invention. The stretch ratio is the linear speed of the fibers after stretching (for example, the linear speed of the roller 42 or a foraminous surface (not shown) divided by the linear speed of the fibers after extrusion. For example, the stretch ratio can be calculated in certain modalities as follows: Stretch Ratio = A / B
[0075] where, A is a linear speed of the fiber after stretching (ie, Godet speed) and is directly measured; and is the linear speed of the extruded fiber and can be calculated as follows: Extruder linear fiber speed = C / (25 * n * D * E2)
[0076] being that, C is the productivity through a single orifice (grams per minute); is the melting density of the polymer (grams per cubic centimeter); and is the diameter of the hole (in centimeters) through which the fiber is extruded. In certain embodiments of the present invention, the stretch ratio can be from about 200: 1 to about 7500: 1, in some embodiments from about 500: 1 to about 6500: 1, and in some embodiments, from about 1000: 1 to about 6000: 1.
[0077] If desired, the fibers collected on roller 42 can optionally be subjected to additional line processing and / or conversion steps (not shown), as will be understood by those skilled in the art. For example, textile fibers can be formed by "cold drawing" the fibers collected at a temperature below their softening temperature to the desired diameter, and therefore frying, texturing, and / or cutting the fibers to the length of desired fiber.
[0078] Regardless of the particular way in which they are formed, the present inventors have found that stretching the fiber significantly increases the axial dimension of the discrete domains reacted so that they have a generally linear, elongated shape. The elongated domains may have an axial dimension that is about 10% or more, in some modalities from about 50% to about 1,000%, and in some modalities, from about 100% to about 500% greater than the axial dimension of the domains before stretching the fiber. The axial dimension after stretching the fiber can, for example, vary from about 10 µm to about 300 µm, in some embodiments from about 40 pm to about 250 µm, and in some embodiments from about 50 µm to about 200 pm. The domains can also be relatively thin and thus have a small dimension in a direction orthogonal to the axial dimension (i.e., cross-sectional dimension). For example, the cross-sectional dimension can be from about 0.02 to about 75 micrometers, in some embodiments from about 0.1 to about 40 micrometers, and in some embodiments, from 0.4 to about 20 micrometers in length. This can result in an aspect ratio for the domains (the ratio of the axial dimension to the cross-sectional dimension) from about 3 to about 200, in some modalities from about 5 to about 100, and in some modalities, from about 5 to about 50.
[0079] The presence of these elongated domains is indicative of the capacity of the thermoplastic composition to absorb the energy transmitted during the stretching of the fiber. In this way, the composition is not as fragile as poly (lactic acid) and in this way it can be released by applying tension instead of fracture. Upon release in tension, the polymer can continue to function as a charge carrying the member even after the fiber has exhibited substantial elongation. In this respect, the fibers of the present invention are capable of exhibiting improved "peak elongation" properties, i.e., the percentage of fiber elongation at its peak load. For example, the fibers of the present invention may exhibit a peak elongation of about 25% or more, in some embodiments about 30% or more, in some embodiments from about 40% to about 350%, and in some embodiments , from about 50% to about 250%. Such stretches can be obtained for fibers having a wide variety of average diameters, such as those ranging from about 0.1 to about 50 micrometers, in some modalities from about 1 to about 40 micrometers, in some modalities from about 2 to about 25 micrometers, and in some embodiments, from about 5 to about 15 micrometers.
[0080] While having the ability to stretch under tension, the fibers of the present invention can also remain relatively strong. A parameter that is indicative of the relative strength of the fibers of the present invention is the "toughness", which indicates the tensile strength of a fiber expressed as strength per unit of linear density. For example, the fibers of the present invention can have a toughness of about 7.35 to about 58.84 mN (about 0.75 to about 6.0 grams-strength ("gf")) per denier, in some modalities from about 9.80 to about 44.13 mN (about 1.0 to about 4.5 gf) per denier, and in some modalities, from about 14.71 to about 39.23 mN (about 1.5 to about 4.0 gf) per denier. The denier of the fibers may vary depending on the desired application. Typically, fibers are formed to have one denier per filament (i.e., the unit of linear density equal to the mass in grams per 9000 meters of fiber) of less than about 6, in some embodiments less than about 3, and in some modalities, from about 0.5 to about 3.
[0081] If desired, the fibers of the present invention can also be formed into a coherent weft structure by randomly depositing the fibers on a forming surface (optionally with the help of a vacuum) and then connecting the resulting weft using any known technique. For example, an endless foraminous forming surface may be positioned below the fiber stretch unit and receive the fibers from an external opening. A vacuum can be positioned below the forming surface to stretch the fibers and consolidate the non-woven non-woven web. Once formed, the nonwoven web can then be bonded using any conventional technique, such as with an adhesive or autogenously (e.g., melting and / or self-adhering the fibers without an external adhesive applied). Autogenous bonding, for example, can be achieved by contacting the fibers at the same time that they are semi-fused or adherent, or simply by combining an adherent resin and / or solvent with the poly (lactic acid) (s) used to form the fibers. Suitable autogenous bonding techniques may include ultrasonic bonding, thermal bonding, bonding through the air, calender bonding, and so on. For example, the weft can also be linked or embossed with a pattern by a thermomechanical process in which the weft is passed between a smooth heated anvil roll and a heated standard roll. The pattern roll can have any high pattern that provides the desired weft appearance or properties. Desirably, the pattern roll defines a high pattern which defines a plurality of bonding sites that define a bonding area between about 2% and 30% of the total roll area. Exemplary connection patterns include, for example, those described in US Patent 3,855,046 to Hansen et al., US Patent No. 5,620,779 to Lew et al., US Patent No. 5,962,112 to Havnes et al., US Patent 6,093 .665 by Savovitz et al., As well as US Patent Application Nos. 428,267 by Romano et al., 390,708 by Brown; 418,305 to Zander, et al; 384,508 to Zander, et al; 384,819 by Zander, and others, 358,035 by Zander, and others, and 315,990 by Blenke, and others, all of which are incorporated herein in their entirety by reference to this for all purposes. The pressure between the rollers can be about 2.3 to about 907.2 kg (about 5 to about 2,000 pounds) per linear inch. The pressure between the rollers and the temperature of the rollers is balanced to obtain the desired weft appearance or properties while maintaining the same properties as the cloth. As is well known to those skilled in the art, the required temperature and pressure can vary depending on many factors including, but not limited to, standard bonding area, polymer properties, fiber properties and nonwoven properties.
[0082] In addition to spunbond wefts, a variety of other non-woven wefts can also be formed from the thermoplastic composition according to the present invention, such as meltblown wefts, linked carded wefts, web wet wefts, airlaid wefts, accommodated wefts , hydraulically tangled wefts, etc. For example, the thermoplastic composition can be extruded through a plurality of capillaries and fine mold in a converging high-speed gas stream (for example, air) that attenuates the fibers to reduce their diameter. Therefore, the meltblown fibers are carried by the high-speed gas stream and are deposited on a collection surface to form a web of randomly dispersed meltblown fibers. Alternatively, the polymer can be formed in a carded web by placing bales of fibers formed from the thermoplastic composition in a catcher that separates the fibers. Then, the fibers are sent through a combing or carding unit which also separates and aligns the fibers in the direction of the machine in order to form a fibrous nonwoven web oriented towards the machine. Once woven, the nonwoven web is typically stabilized by one or more known binding techniques.
[0083] If desired, the nonwoven web can also be a composite that contains a combination of fibers of thermoplastic composition and other types of fibers (for example, textile fibers, filaments, etc.). For example, additional synthetic fibers can be used, such as those formed from polyolefins, for example, polyethylene, polypropylene, polybutylene, and so on; polytetrafluoroethylene; polyesters, for example, polyethylene terephthalate and so on; polyvinyl acetate; polyvinyl chloride acetate; polyvinyl butyral; acrylic resins, for example, polyacrylate, polymethylacrylate, polymethylmethacrylate, and so on; polyamides, for example, nylon; polyvinyl chloride; polyvinylidene chloride; polystyrene; polyvinyl alcohol; polyurethanes; poly (lactic acid); etc. If desired, biodegradable polymers, such as poly (glycolic) (PGA), poly (lactic) acid (PLA), poly (p-malic) (PMLA), poly (8-caprolactone) (PCL), poly ( p-dioxanone) (PDS), poly (butylene) succinate (PBS), and poly (3-hydroxybutyrate) (PHB), can also be used. Some Examples of known synthetic fibers include two-core sheath fibers available from KoSa Inc. of Charlotte, North Carolina under the designations T-255 and T-256, both of which use a polyolefin sheath, or T-254, which it has a low-melting co-polyester sheath. Still other known bicomponent fibers that can be used include those available from Chisso Corporation of Moriyama, Japan or Fibervisions LLC of Wilmington, Delaware, USA. Poly (lactic acid) textile fibers can also be used, such as those commercially available from Far Eastern Textile, Ltd. of Taiwan.
[0084] The composite may also contain pulp fibers, such as medium high fiber length pulp, medium low fiber length pulp, or combinations thereof. An Example of suitable fluffy pulp fibers of medium high length includes kraft softwood pulp fibers. Kraft softwood pulp fibers are derived from coniferous trees and include pulp fibers such as, but not limited to, softwood species from the north, west, and south, including redwood, red cedar, hemlock, Douglas fir , real firs, pine (for example, southern pines), fir (for example, black fir), bamboo, combinations thereof, and so on. Northern Kraft softwood pulp fibers can be used in the present invention. An Example of commercially available Southern Kraft softwood pulp fibers suitable for use in the present invention includes those available from Weyerhaeuser Company with offices in Federal Way, Washington under the trade name "NF-405". Another pulp suitable for use in the present invention is a bleached, sulphate wood pulp containing mainly soft wood fibers which are available from Bowater Corp. with offices in Greenville, South Carolina under the trade name CoosAbsorb S. pulp. Medium-low fibers can also be used in the present invention. An Example of suitable low medium length pulp fibers is hardwood Kraft pulp fibers. Hardwood Kraft pulp fibers are derived from deciduous trees and include pulp fibers such as, but not limited to, eucalyptus, maple, birch, poplar, etc. Eucalyptus kraft pulp fibers may be particularly desired to increase softness, enhance gloss, increase opacity, and change the pore structure of the sheet to increase its twisting capacity. Bamboo or cotton fibers can also be used.
[0085] Nonwoven composites can be formed using a variety of known techniques. For example, the nonwoven composite may be an "accommodated material" that contains a stabilized combination or mold of the thermoplastic composition fibers and an absorbent material. As an Example, the accommodated materials can be made by a process in which at least one meltblown mold head is arranged next to a chute through which absorbent materials are added to the web at the same time as it is forming. Such absorbent materials may include, but are not limited to, pulp fibers, superabsorbent particles, inorganic and / or organic absorbent materials, treated polymeric textile fibers, and so on. The relative percentages of the absorbent material can vary over a wide range depending on the desired characteristics of the nonwoven composite. For example, the non-woven composite may contain from about 1% by weight to about 60% by weight, in some embodiments from 5% by weight to about 50% by weight, and in some embodiments, from about 10% by weight to about 40% by weight of fibers of thermoplastic composition. The non-woven composite can likewise contain from about 40% by weight to about 99% by weight, in some embodiments from 50% by weight to about 95% by weight, and in some embodiments, from about 60% by weight to about 90% by weight of absorbent material. Some examples of such accommodated materials are described in U.S. Patent Nos. 4,100,324 to Anderson, et al; 5,284,703 to Everhart, and others; and 5,350,624 by Georger, et al .; which are incorporated herein in their entirety by reference to this for all purposes.
[0086] Non-woven laminates can also be formed in the present invention in which one or more layers are formed from the thermoplastic composition. For example, the nonwoven web of one layer can be a spunbond containing the thermoplastic composition, while the nonwoven web of another layer contains thermoplastic composition, another biodegradable polymer (s), and / or any other polymer ( for example, polyolefins). In one embodiment, the nonwoven laminate contains a meltblown layer positioned between two layers of spunbond to form a spunbond / meltblown / spunbond laminate ("SMS"). If desired, the spunbond layer can be formed from the thermoplastic composition. The meltblown layer can be formed from the thermoplastic composition, another biodegradable polymer (s), and / or any other polymer (for example, polyolefins). Various techniques for forming the SMS laminates are described in U.S. Patent Nos. 4,041,203 to Brock et al; 5,213,881 to Timmons, and others; 5,464,688 to Timmons, and others; 4,374,888 to Bornslaeger; 5,169,706 by Collier, et al .; and 4,766,029 to Brock et al., as well as U.S. Patent Application Publication No. 2004/0002273 to Fitting, et al., all of which are incorporated herein in their entirety by reference to this for all purposes. Certainly, the non-woven laminate can have another configuration and has any desired number of meltblown and spunbond layers, such as spunbond / meltblown / meltblown / spunbond ("SMMS") laminates, spunbond / meltblown ("SM") laminates, etc. Although the weight of the non-woven laminate can be adapted to the desired application, it generally ranges from about 10 to about 300 grams per square meter ("g / m2"), in some embodiments from about 25 to about 200 g / m2 , and in some embodiments, from about 40 to about 150 g / m2.
[0087] If desired, the laminate or nonwoven weave can be applied with various treatments to convey desirable characteristics. For example, the web can be treated with liquid repellant additives, antistatic agents, surfactants, dyes, anti-browning agents, fluorochemical alcohol or blood repellents, lubricants, and / or antimicrobial agents. In addition, the weft can be subjected to an electrical treatment that transmits an electrostatic charge to improve filtration efficiency. The charge may include layers of positive or negative charges attached to or near the surface of the polymer, or charge clouds stored in most of the polymer. The charge may also include polarization charges that are frozen in alignment with the molecules' dipoles. Techniques for subjecting a fabric to electrical treatment are well known to those skilled in the art. Examples of such techniques include, but are not limited to, thermal, liquid contact, electronic beam and corona discharge techniques. In a particular embodiment, electrical treatment is a corona discharge technique, which involves subjecting the laminate to a pair of electrical fields that have opposite polarities. Other methods for forming an electrical material are described in U.S. Patent Nos. 4,215,682 to Kubik, and others; 4,375,718 to Wadsworth; 4,592,815 to Nakao; 4,874,659 to Ando; 5,401,446 to Tsai. and others; 5,883,026 by Reader, et al: 5,908,598 by Rousseau, et al; 6,365,088 to Knight, et al., Which are incorporated herein in their entirety by reference to this for all purposes. V. Articles
[0088] The nonwoven weave can be used in a wide variety of applications. For example, the weft can be incorporated into a "medical product", such as garments, surgical dressings, facial masks, caps in general, surgical caps, slippers, sterilization packages, heating covers, heating pads, and so on . Of course, the nonwoven weave can also be used in several other articles. For example, the nonwoven web can be incorporated into an "absorbent article" that is capable of absorbing water or other fluids. Examples of some absorbent items include, but are not limited to, absorbent personal care items, such as disposable diapers, treatment pants, absorbent underwear, incontinence items, feminine hygiene products (eg sanitary napkins), clothing for swimming, baby wipes, mittens, and so on; medical absorbent articles, such as clothing, fenestration materials, linings, bed pillows, bandages, absorbent linings and medical wipes; food service wipes; clothing items; pockets, and so on. Suitable materials and processes for forming such articles are well known to those skilled in the art. Absorbent articles, for example, typically include a substantially liquid-impermeable layer (e.g., outer covering), liquid-permeable layer (e.g., body-side lining, compensation layer, etc.), and an absorbent core. In one embodiment, for example, the nonwoven web formed in accordance with the present invention can be used to form an outer covering of an absorbent article. If desired, the nonwoven web can be laminated to a liquid impermeable film which is either vapor permeable or vapor impermeable.
[0089] The present invention can be better understood with reference to the following examples. In each of the examples below, poly (lactic acid) was dried in a desiccant at a temperature of about 77 ° C before combining with the polyepoxide modifier. The resulting combination was also dried in a desiccant dryer at a temperature of 522C to 662C (1252F to 150 ° F) before spinning the fiber. EXAMPLE 1
[0090] The fibers formed from 100% poly (lactic acid) (PLA) were formed as a control by extruding PLA 6201D (Natureworks®, 10 g / 10 min melt flow rate at 190 ° C) as fiber. More specifically, poly (lactic acid) was supplied to an extruder heated to a temperature of 235 ° C. The extruder capacity was 0.4 grams per hole per minute (in a 16-hole per inch spinning package). The melt was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by an insufflator at a temperature of 25 ° C. The continuous fibers were then stretched through a fiber stretching unit and sent on a roller at a speed of 2,000 meters per minute ("m / min"). The resulting stretch ratio was 1549. The fibers were collected at 2,000 m / min to provide a target fiber of 15 µm. The fibers were then stretched on a roller at a speed of 3,000 meters per minute ("m / min"). The resulting stretch ratio was 2,324. EXAMPLE 2
[0091] The ability to form fibers from a combination of 97% by weight of poly (lactic acid) (PLA 6201D, Natureworks®) and 3% by weight of a polyepoxide modifier has been demonstrated. The polyepoxide modifier was poly (ethylene-methylacrylate-glycidyl methacrylate) (Sigma-Aldrich Co.) having a melt flow rate of 6 g / 10 min (190 ° C / 2,160 g), a content of glycidyl methacrylate of 8% by weight, methyl acrylate content of 25% by weight, and ethylene content of 67% by weight. The polymers were fed into a Thermo Prismrm USALAB 16 twin-screw extruder (Thermo Electron Corp., Stone, England). The melting temperature of the extruder was 195 ° C. The extruder had 11 zones, numbered consecutively 0-10 from the feed hopper to the mold. The poly (lactic acid) resin was combined dry with the polyepoxide modifier and fed to the extruder feed channel (unheated, before zone 1 of the extruder) at a rate of 1.36 kg (3 pounds) per hour. The screw speed was 200 revolutions per minute ("rpm"). The mold used to extrude the resin had 1 mold opening (3 mm in diameter). Under formation, the extruded resin was cooled on a fan-cooled conveyor belt and formed into pellets. The pellets were then supplied to an extruder heated to a temperature of 240 ° C. The extruder capacity was 0.4 grams per hole per minute (in a 16-hole per inch spinning package). The fusion was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by an insufflator at a temperature of 25 ° C. The continuous fibers were then stretched on a roller at a speed of 2,000 meters per minute ("m / min"). The resulting stretch ratio was 1,549. EXAMPLE 3
[0092] The fibers were formed from a combination of 95% by weight of poly (lactic acid) (PLA 6201D, Natureworks®) and 5% by weight of poly (ethylene methyl co-acrylate-glycidyl methacrylate) (Siyma-Aldrich Co.) as described in Example 2. The continuous fibers were then stretched on a roller at a speed of 2,000 meters per minute ("m / min"). The resulting stretch ratio was 1,549. The fibers were also spun at 3,000 meters per minute ("m / min") for a resulting stretch ratio of 2,324. EXAMPLE 4
[0093] The fibers were formed from a combination of 90% by weight of poly (lactic acid) (PLA 6201D, Natureworks®) and 10% by weight of poly (ethylene methyl co-acrylate-glycidyl methacrylate) (Sigma-Aldrich Co.) as described in Example 2, except that the fibers were extruded at 215 ° C and stretched on a roller at 500 m / min with a resulting stretch ratio of 387. Before fiber formation, electron microscopy ("TEM") was also used to visualize the combination. An image of the 10,000X combination is shown in Figure 2. As shown, the combination contains a plurality of small domains as evidenced by the dark areas. EXAMPLE 5
[0094] The pellets were formed from a combination of 85% by weight of poly (lactic acid) (PLA 6201D, Natureworks®) and 15% by weight of poly (ethylene-methylacrylate-glycidyl methacrylate) (Sigma-Aldrich Co.) as described in Example 2. The resulting pellets were not spun fibers. EXAMPLE 6
[0095] The fibers were formed from a combination of 90% by weight of poly (lactic acid) (PLA 6201D, Natureworks®) and 10% by weight of a polyepoxide modifier. The polyepoxide modifier was poly (ethylene-methyl co-acrylate-glycidyl co-methacrylate) (Lotader® AX8950, Arkema) having a melt flow rate of 70-100 g / 10 min (190 ° C / 2,160 g) , a glycidyl methacrylate content of 7 to 11% by weight, a methyl acrylate content of 13 to 17% by weight, and an ethylene content of 72 to 80% by weight. The same process was used as in Example 2, except that the fibers were extruded at 210 ° C and stretched on a roller at a speed of 800 m / min resulting in a stretch ratio of 620. EXAMPLE 7
[0096] The pellets were formed from a combination of 90% by weight of poly (lactic acid) (PLA 6201D, Natureworks®) and 10% by weight of poly (ethylene methyl co-acrylate-glycidyl methacrylate) (Sigma-Aldrich Co.) as described in Example 2, except that the polymers were combined together at a melting temperature of 235 ° C. The resulting pellets were not spun fibers.
[0097] Ten (10) samples were taken according to Examples 1-4 and 6 and then tested for toughness and elongation. The results (average) are shown below. Table 1: Fiber Properties for Examples 1-4 and 6
EXAMPLE 8
[0098] The ability to form fibers from a combination of 88.7% by weight of poly (lactic acid) (PLA 6201D, Natureworks®), 1.5% by weight of a polyepoxide modifier, and 9.8% by weight weight of a stiffening additive has been demonstrated. The polyepoxide modifier was poly (ethylene-methyl co-acrylate-glycidyl co-methacrylate) (Lotader® AX8950, Arkema). The stiffening additive was VistamaxxlM 2120 (Exxonmobil), which is a polyolefin / elastomer copolymer with a melt flow rate of 29 g / 10 min (190 ° C, 2,160 g) and a density of 0.866 g / cm3. The polymers were fed and a co-rotating, twin-screw extruder (ZSK-30, diameter 30 mm, length 1328 mm) was used for the composition that was manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey, USA. The extruder had 14 zones, numbered consecutively 1-14 from the hopper to the mold. The first No. 1 drum received the resins through a gravimetric feeder in a total capacity of 6.80 kg (15 pounds) per hour. The mold used to extrude the resin had 3 mold openings (6 mm in diameter) that were separated by 4 mm. In the formation, the extruded resin was cooled on a conveyor belt cooled by a fan and formed into pellets by a Conair pelletizer. The screw speed was 100 revolutions per minute ("rpm"). The pellets were then supplied to an extruder heated to a temperature of 220 ° C. The extruder capacity was 0.4 grams per hole per minute (in a 16-hole per inch spinning package). The melt was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by a blower at a temperature of 25 ° C. The continuous fibers were then stretched on a roller at a speed of 1,000 meters per minute ("m / min"). The resulting stretch ratio was 775. EXAMPLE 9
[0099] The fibers were formed as described in Example 8, except that the temperature at which the fibers were extruded was 240 ° C and the speed of drawing the roller was 1,000 meters per minute ("m / min"). The resulting stretch ratio was 775. EXAMPLE 10
[00100] The fibers were formed as described in Example 8, except that the stiffening additive was EscoreneTM Ultra 7720 (Exxonmobil), which is an ethylene vinyl acetate ("EVA") resin, which has a melt flow rate 150 g / 10min and a density of 0.946 g / cm3 and the roller stretching speed was 700 meters per minute ("m / min"). The resulting stretch ratio was 542. EXAMPLE 11
[00101] The fibers were formed as described in Example 10, except that the temperature at which the fibers were extruded was 240 ° C and the roller drawing speed was 1,000 meters per minute ("m / min"). The resulting stretch ratio was 775. EXAMPLE 12
[00102] The fibers were formed as described in Example 10, except that the temperature at which the fibers were extruded was 230 ° C. EXAMPLE 13
[00103] The fibers were formed as described in Example 8, except that the temperature at which the polymers were combined was 235 ° C and the temperature at which the fibers were extruded was 235 ° C and the roller drawing speed was 3,000 meters per minute ("m / min"). The resulting stretch ratio was 2,324.
[00104] Ten (10) samples were taken according to Examples 8-13 and then tested for toughness and elongation. The results (average) are shown below. Table 2: Fiber Properties for Examples 8-13
EXAMPLE 14
[00105] The ability to form fibers from a combination of 89.6% by weight of poly (lactic acid) (PLA 6201D, Natureworks®), 0.5% by weight of a polyepoxide modifier, and 9.9% by weight weight of a stiffening additive has been demonstrated. The polyepoxide modifier was poly (ethylene-methyl co-acrylate-glycidyl co-methacrylate) (Lotader® AX8950, Arkema). The stiffening additive was VistamaxxrM 2120 (Exxonmobil). The polymers that were fed into a co-rotating, twin-screw extruder (ZSK-30, diameter 30 mm, length 1,328 mm) were used for the composition that was manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey, USA . The extruder had 14 zones, numbered consecutively 1-14 from the hopper to the mold. The first No. 1 drum received the resins through the gravity feeder at a total capacity of 6.80 kg (15 pounds) per hour. The mold used to extrude the resin had 3 mold openings (6mm in diameter) that were separated by 4mm. In formation, the extruded resin was cooled on a conveyor belt cooled by a fan and formed into pellets by a Conair pelletizer. The screw speed was 100 revolutions per minute ("rpm"). The pellets were then supplied to an extruder heated to a temperature of 220 ° C. The extruder capacity was 0.4 grams per hole per minute (in a 16-hole per inch spinning package). The fusion was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by an insufflator at a temperature of 25 ° C. The continuous fibers were then stretched on a roller at a speed of 500 meters per minute ("m / min"). The resulting stretch ratio was 387. The fibers could not be collected. EXAMPLE 15
[00106] The fibers were formed as described in Example 14, except that the temperature at which the fibers were extruded was 225 ° C and the roller speed was 750 m / min. The fibers could not be collected. EXAMPLE 16
[00107] The fibers were formed as described in Example 14, except that the temperature at which the fibers were extruded was 230 ° C and the roller speed was 1,500 m / min. The fibers could not be collected. EXAMPLE 17
[00108] The fibers were formed as described in Example 14, except that the temperature at which the fibers were extruded was 235 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 18
[00109] The fibers were formed as described in Example 14, except that the temperature at which the fibers were extruded was 240 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 19
[00110] The fibers were formed as described in Example 14, except that the temperature at which the fibers were extruded was 245 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 2,800 m / min. EXAMPLE 20
[00111] The fibers were formed as described in Example 14, except that the temperature at which the fibers were extruded was 250 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 2,900 m / min.
[00112] Ten (10) samples were taken according to Examples 17-20 and then tested for toughness and elongation. The results (average) are shown below. Table 3: Fiber Properties for Examples 17-20
EXAMPLE 21
[00113] The ability to form fibers from a combination of 88.7% by weight of poly (lactic acid) (PLA 6201D, Natureworks®), 1.5% by weight of a polyepoxide modifier, and 9.8% by weight weight of a stiffening additive has been demonstrated. The polyepoxide modifier was poly (ethylene-methyl co-acrylate-glycidyl co-methacrylate) (Lotader® AX8950, Arkema). The stiffening additive was VistamaxxTM 2120 (Exxonmobil). The polymers that were fed into a co-rotating, twin-screw extruder (ZSK-30, diameter 30 mm, length 1,328 mm) were used for the composition that was manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey, USA . The extruder had 14 zones, numbered consecutively 1 -14 from the feed hopper to the mold. The first No. 1 drum received the resins through the gravimetric feeder in a total capacity of 6.80 kg (15 pounds) per hour. The mold used to extrude the resin had 3 mold openings (6mm in diameter) that were separated by 4mm. In formation, the extruded resin was cooled on a conveyor belt cooled by a fan and formed into pellets by a Conair pelletizer. The screw speed was 100 revolutions per minute ("rpm"). The pellets were then supplied to an extruder heated to a temperature of 220 ° C. The extruder capacity was 0.4 grams per hole per minute (in a 16-hole per inch spinning package). The fusion was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by a blower at a temperature of 25 ° C. The continuous fibers were then stretched on a roller at a speed of 500 meters per minute ("m / min"). The resulting stretch ratio was 387. The fibers could not be collected. EXAMPLE 22
[00114] The fibers were formed as described in Example 21, except that the temperature at which the fibers were extruded was 225 ° C and the roller speed was 1,200 m / min. The fibers could not be collected. EXAMPLE 23
[00115] The fibers were formed as described in Example 21, except that the temperature at which the fibers were extruded was 230 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 2,400 m / min. EXAMPLE 24
[00116] The fibers were formed as described in Example 21, except that the temperature at which the fibers were extruded was. 235 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 25
[00117] The fibers were formed as described in Example 21, except that the temperature at which the fibers were extruded was 240 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 26
[00118] The fibers were formed as described in Example 21, except that the temperature at which the fibers were extruded was 245 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 27
[00119] The fibers were formed as described in Example 21, except that the temperature at which the fibers were extruded was 250 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 2,800 m / min.
[00120] Ten (10) samples were taken according to Examples 23-27 and then tested for toughness and elongation. The results (average) are shown below. Table 4: Fiber Properties for Examples 23-27
EXAMPLE 28
[00121] The ability to form fibers from a combination of 87.8% by weight of poly (lactic acid) (PLA 6201D, Natureworks0), 2.4% by weight of a polyepoxide modifier, and 9.8% by weight of a stiffening additive has been demonstrated. The polyepoxide modifier was poly (ethylene-methyl co-acrylate, glycidyl methacrylate) (Lotader® AX8950, Arkema). The stiffening additive was VistamaxxTM 2120 (Exxonmobil). The polymers that were fed into a co-rotating, twin-screw extruder (ZSK-30, diameter 30 mm, length 1,328 mm) were used for the composition that was manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey, USA . The extruder had 14 zones, numbered consecutively 1-14 from the hopper to the mold. The first No. 1 drum received the resins through the gravity feeder in a total capacity of 6.80 kg (15 pounds) per hour. The mold used to extrude the resin had 3 mold openings (6mm in diameter) that were separated by 4mm. In formation, the extruded resin was cooled on a conveyor belt cooled by a fan and formed into pellets by a Conair pelletizer. The screw speed was 100 revolutions per minute ("rpm"). The pellets were then supplied to an extruder heated to a temperature of 220 ° C. The extruder capacity was 0.4 grams per hole per minute (in a 16-hole per inch spinning package). The fusion was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by an insufflator at a temperature of 25 ° C. The continuous fibers were then stretched on a roller at a speed of 1,300 meters per minute ("m / min"). The resulting stretch ratio was 387. The fibers could not be collected. EXAMPLE 29
[00122] The fibers were formed as described in Example 28, except that the temperature at which the fibers were extruded was 225 ° C and the roller speed was 1,500 m / min. The fibers could not be collected. EXAMPLE 30
[00123] The fibers were formed as described in Example 28, except that the temperature at which the fibers were extruded was 230 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 31
[00124] The fibers were formed as described in Example 28, except that the temperature at which the fibers were extruded was 235 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 2,900 m / min. EXAMPLE 32
[00125] The fibers were formed as described in Example 28, except that the temperature at which the fibers were extruded was 240 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 33
[00126] The fibers were formed as described in Example 28, except that the temperature at which the fibers were extruded was 245 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 34
[00127] The fibers were formed as described in Example 28, except that the temperature at which the fibers were extruded was 250 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 2,800 m / min.
[00128] Ten (10) samples were taken according to Examples 30-34 and then tested for toughness and elongation. The results (average) are shown below. Table 5: Fiber Properties for Examples 30-34
EXAMPLE 35
[00129] The ability to form fibers from a combination of 88.7% by weight of poly (lactic acid) (PLA 6201D, Natureworks @), 1.5% by weight of a polyepoxide modifier, and 9.8% by weight weight of a stiffening additive has been demonstrated. The polyepoxide modifier was poly (ethylene-methyl co-acrylate-glycidyl co-methacrylate) (Lotader® AX8950, Arkema). The stiffening additive was VistamaxxTM 2120 (Exxonmobil). The polymers that were fed into a co-rotating, twin-screw extruder (ZSK-30, diameter 30 mm, length 1,328 mm) were used for the composition that was manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey, USA . The extruder had 14 zones, numbered consecutively 1-14 from the hopper to the mold. The first No. 1 drum received the resins through a gravimetric feeder in a total capacity of 6.80 kg (15 pounds) per hour. The mold used to extrude the resin had 3 mold openings (6mm in diameter) that were separated by 4mm. In formation, the extruded resin was cooled on a conveyor belt cooled by a fan and formed into pellets by a Conair pelletizer. The screw speed was 200 revolutions per minute ("rpm"). The pellets were then supplied to an extruder heated to a temperature of 220 ° C. The extruder capacity was 0.4 grams per hole per minute (in a 16-hole per inch spinning package). The fusion was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by an insufflator at a temperature of 25 ° C. The continuous fibers were then stretched on a roller at a speed of 2,000 meters per minute ('m / min "). The resulting stretch ratio was 1,547. The fibers were collected and then the roller was increased to 3,000 m / min. EXAMPLE 36
[00130] The fibers were formed as described in Example 35, except that the temperature at which the fibers were extruded was 230 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 37
[00131] The fibers were formed as described in Example 35, except that the temperature at which the fibers were extruded was 235 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 38
[00132] The fibers were formed as described in Example 35, except that the temperature at which the fibers were extruded was 240 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 39
[00133] The fibers were formed as described in Example 35, except that the temperature at which the fibers were extruded was 245 ° C and the roller speed was 2,000 m / min. EXAMPLE 40
[00134] The fibers were formed as described in Example 35, except that the temperature at which the fibers were extruded was 250 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 41
[00135] The fibers were formed as described in Example 35, except that the temperature at which the fibers were extruded was 255 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min.
[00136] Ten (10) samples were taken according to Examples 35-41 and then tested for toughness and elongation. The results (average) are shown below. Table 6: Fiber Properties for Examples 35-41
EXAMPLE 42
[00137] Fibers made from a combination of 88.7% by weight of poly (lactic acid). (PLA 6201D, Natureworks®), 9.8% by weight of a stiffening additive, and 1.5% by weight of a polyepoxide modifier were also employed. The polyepoxide modifier was poly (ethylene-methyl co-acrylate-glycidyl cometacrylate) (Lotader® AX8950, Arkema). The stiffening additive was PP 3155 (Exxonmobil), a polypropylene homopolymer. The polymers were fed into a dual-spindle cogiratory extruder (ZSK-30, diameter 30 mm, length 1,328 mm) were used for the composition that was manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey, USA. The extruder had 14 zones, numbered consecutively 1-14 from the hopper to the mold. The first No. 1 drum received the resins through a gravimetric feeder in a total capacity of 6.80 kg (15 pounds) per hour. The mold used to extrude the resin had 3 mold openings (6mm in diameter) that were separated by 4mm. In formation, the extruded resin was cooled on a conveyor belt cooled by a fan and formed into pellets by a Conair pelletizer. The screw speed was 100 revolutions per minute ("rpm"). The pellets were then supplied to an extruder heated to a temperature of 230 ° C. The extruder capacity was 0.4 grams per hole per minute (in a 16-hole per inch spinning package). The fusion was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by an insufflator at a temperature of 25 ° C. The continuous fibers were then stretched on a roller at a speed of 2,000 meters per minute ("m / min"). The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 43
[00138] The fibers were formed as described in Example 42, except that the temperature at which the fibers were extruded was 235 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min. EXAMPLE 44
[00139] The fibers were formed as described in Example 42, except that the temperature at which the fibers were extruded was 240 ° C and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and the fibers were spun up to 3,000 m / min.
[00140] Ten (10) samples were taken according to Examples 42-44 and then tested for toughness and elongation. The results (average) are shown below. Table 7: Fiber Properties for Examples 42-44
EXAMPLE 45
[00141] The ability to form fibers from a combination of 89.25% by weight of poly (lactic acid) (PLA 6201D, Natureworks0), 0.75% by weight of a polyepoxide modifier, and 10% by weight of a stiffening additive has been demonstrated. The polyepoxide modifier was poly (ethylene-methyl co-acrylate-glycidyl methacrylate) (Lotader® AX8900, Arkema). The stiffening additive was PP 3155 (Exxon-Mobil), a polypropylene homopolymer. The polymers that were fed into a co-rotating, twin-screw extruder (ZSK-30, diameter 30 mm, length 1,328 mm) were used for the composition that was manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey, USA . The extruder had 14 zones, numbered consecutively 1-14 from the hopper to the mold. The first No. 1 drum received the resins through a gravimetric feeder in a total capacity of 6.80 kg (15 pounds) per hour. The mold used to extrude the resin had 3 mold openings (6mm in diameter) that were separated by 4mm. In formation, the extruded resin was cooled on a conveyor belt cooled by a fan and formed into pellets by a Conair pelletizer. The screw speed was 200 revolutions per minute ("rpm"). In formation, the extruded resin was cooled on a fan-cooled conveyor belt and formed into pellets. The pellets were then supplied to an extruder heated to a temperature of 240 ° C. The extruder capacity was 0.4 grams per hole per minute (in a 16-hole per inch spinning package). The fusion was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by an insufflator at a temperature of 25 ° C. The continuous fibers were then stretched on a roller at a speed of 2,000 meters per minute ("m / min"). The resulting stretch ratio was 1,547. The fibers were collected and then the roller was increased to 3,000 m / min. The extruder capacity was then decreased to 0.28 grams per hole per minute and the fibers were stretched on a roller at 3,000 m / min resulting in a 3,320 stretch ratio. EXAMPLE 46
[00142] The fibers were formed as described in Example 45, except that the temperature at which the fibers were extruded was 245 ° C and the roller speed was 2,000 m / min. The fibers were not collected. EXAMPLE 47
[00143] The fibers were formed as described in Example 45, except that the temperature at which the fibers were extruded was 250 ° C and the roll speed was 2,000 m / min. The fibers were not collected. EXAMPLE 48
[00144] The fibers were formed as described in Example 45, except that the concentration of LotaderTM AX8900 was 0.5% and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and spun up to 3,000 m / min in a capacity of 0.16 grams per hole per minute resulting in a stretch ratio of 5,810. EXAMPLE 49
[00145] The fibers were formed as described in Example 45, except that the polypropylene concentration was 2.5% and the roller speed was 2,000 m / min. The fibers were collected at 2,000 m / min and spun up to 3,000 m / min in a capacity of 0.24 grams per hole per minute resulting in a stretching ratio of 3,873. Before the formation of the fibers, transmission electron microscopy ("TEM") was also employed to visualize the combination. An image of the 10,000x combination is shown in Figure 3. As shown, the combination contains a plurality of Lotader® AX 8900 nano-sized domains as evidenced by the smaller dark areas and also a plurality of micro-sized polypropylene domains as evidenced through the larger dark areas. EXAMPLE 50
[00146] The fibers were formed as described in Example 45, except that a polyepoxide modifier was CESA Extend 8478 (Clariant Corporation, 10% BASF Joncryl / m ADR 4368 reduced in Natureworks PLA 6201D) and the CESA concentration was 0, 5% by weight and the roller speed was 2,000 m / min resulting in a stretch ratio of 1,549. The fibers were not collected.
[00147] Before the formation of fibers, transmission electron microscopy ("TEM") was also employed to visualize the combination. An image of the 10,000X combination is shown in Figure 4. As shown, the combination contains a plurality of large domains as evidenced by the dark areas. Ten (10) fiber samples were also taken according to Examples 45, 48, and 49. and then tested for toughness and elongation. The results (average) are shown below. Table 8: Fiber Properties for Examples 45 and 48-49
EXAMPLE 51
[00148] The ability to form fibers from a combination of 98.5% by weight of poly (lactic acid) (PLA 6201D, Natureworks®), 1.5% by weight of a polyepoxide modifier. The polyepoxide modifier was poly (ethylene-methyl co-acrylate-glycidyl co-methacrylate) (Lotader® AX8900, Arkema). The polymers that were fed into a co-rotating, twin-screw extruder (ZSK-30, diameter 30 mm, length 1,328 mm) were used for the composition that was manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey, USA . The extruder had 14 zones, numbered consecutively 1-14 from the hopper to the mold. The first No. 1 drum received the resins through a gravimetric feeder in a total capacity of 6.80 kg (15 pounds) per hour. The mold used to extrude the resin had 3 mold openings (6mm in diameter) that were separated by 4mm. In formation, the extruded resin was cooled on a conveyor belt cooled by a fan and formed into pellets by a Conair pelletizer. The screw speed was 200 revolutions per minute ("rpm"). In formation, the extruded resin was cooled on a fan-cooled conveyor belt and formed into pellets. The pellets were then supplied to an extruder heated to a temperature of 240 ° C. The extruder capacity was 0.4 grams per hole per minute (in a spinning package of 16 holes per inch). The fusion was extruded through the spinning package to form continuous fibers which were then passed through heat shock (quenched) using forced air supplied by an insufflator at a temperature of 25 ° C. The continuous fibers were then stretched on a roller at a speed of 2,000 meters per minute ("m / min"). The resulting stretch ratio was 1,547. The fibers were not collected, however, the roller was increased to 3,000 m / min. The extruder capacity was then decreased to 0.28 grams per hole per minute and the fibers were stretched on a roller at 3,000 m / min resulting in a 3,320 stretch ratio.
[00149] Before the formation of fibers, transmission electron microscopy ("TEM") was also used to visualize the combination. An image of the 10,000X combination is shown in Figure 5. As shown, the combination contains a plurality of Lotader® AX 8900 nano-sized domains as evidenced by the smaller dark areas. EXAMPLE 52
[00150] The fibers were formed as described in Example 51, except that the concentration of Lotader® AX8900 was 0.5% and the roller speed was 2,000 m / min.
[00151] The fibers were collected at 2,000 m / min and spun up to 3,000 m / min in a capacity of 0.16 grams per hole per minute resulting in a stretch ratio of 5,810. Ten (10) samples were prepared according to Example 52 and then tested for toughness and elongation. The results (average) are shown below. Table 9: Fiber Properties for Example 52
EXAMPLE 53
[00152] The ability to form spunbond wefts from fibers made from a combination of 88.7% by weight of poly (lactic acid) (PLA 6201D, Natureworks®), 9.8% by weight PP3155 (Exxon- Mobil) and 1.5% by weight of a polyepoxide modifier. The polyepoxide modifier was poly (ethylene-methylacrylate-glycidyl methacrylate) (Lotader® AX8950, Arkema). The polymers were fed into a double-spindle, coiled, twisting extruder (64 mm, 2,240 mm in length). The extruder had 8 zones, numbered consecutively 1-8 from the hopper to the mold. The first No. 1 drum received the resins through a gravimetric feeder in a total capacity of 249.48 kg (550 pounds) per hour. The mold used to extrude the resin had 24 mold openings (3 millimeters in diameter). In formation, the extruded resin was cooled in water and pelleted using a Gala Underwater pelletizer. The screw speed was 350 revolutions per minute ("rpm"). The pellets were then supplied to an extruder heated to a temperature of 240 ° C. The extruder capacity was 0.7 grams per orifice per minute (0.6 mm aperture, in a 100 orifice per inch spinning package). The fusion was extruded through the spinning package to form continuous fibers which were then passed through thermal shock (quenched) using forced air supplied by an insufflator at a temperature of 25 ° C. The continuous fibers were then mechanically drawn using a fiber drawing unit and deposited on a mobile forming wire at a resulting drawing speed of 4,600 meters per minute and a drawing ratio of 2,025. The fibers were then thermally bonded to form a continuous spunbond web using a heated calender roll. The resulting plot was collected in a winder and evaluated. EXAMPLE 54
[00153] Spunbond wefts were formed as described in Example 53, except that a polymer combination was a plasticized PLA consisting of 92% by weight of poly (lactic acid) (PLA 6201D, Natureworks®), 2% by weight of Pluriol WI-285 (BASF), 2.7% by weight of Carbowax 8000 (Dow) and 3.3% by weight of Fusabond MD-353D (DuPont) and the stretching speed was 3,200 m / min resulting in a ratio stretch of 1,410. The resulting frames were collected in the winder for evaluation. EXAMPLE 55
[00154] The spunbond wefts were formed as described in Example 53, except that your polymer was 100% by weight of poly (lactic acid) (PLA 6201D, Natureworks®), which was not combined and the drawing speed was 3,400 m / min (0.35 mm opening in packs of 100 holes per inch) resulting in a stretch ratio of 509. The resulting frames were collected in the winder for evaluation.
[00155] Ten (10) samples were taken according to Examples 53-55 and then tested for tensile strength and elongation both in the machine (MD) and in the transverse (CD) directions of the web. The results (average) are shown below. The tensile strengths were normalized for the grammage because it is responsible for the differences in grammage.Table 10: Fiber Properties for Examples 53-55

[00156] Although the invention has been described in detail with respect to specific modalities of the same, it will be appreciated that those skilled in the art, when they reach an understanding of the above, will be able to readily conceive changes to, variations of and equivalent to these modalities. Consequently, the scope of the present invention must be assessed as that of the appended claims and any equivalents thereof.

权利要求:
Claims (14)
[0001]
1. A method for forming a poly (lactic acid) fiber, characterized in that it comprises: combining a poly (lactic acid) by melting with a polyepoxide modifier and a polymeric stiffening additive to form a thermoplastic composition, in which the melting combination occurs at a temperature above the melting point of the poly (lactic acid) and below the temperature of 230 ° C, the polyepoxide modifier having an average numerical molecular weight of 7,500 to 250,000 grams per mol, with the amount of the polyepoxide modifier is 0.01% by weight to 10% by weight, based on the weight of the poly (lactic acid); then, extrude the thermoplastic composition at a temperature above 230 ° C to facilitate the reaction of the polyepoxide modifier with the poly (lactic acid); and passing the reacted composition through a mold to form a fiber; wherein the polymeric stiffening additive is a polyolefin.
[0002]
2. Method according to claim 1, characterized by the fact that the polyepoxide modifier includes an epoxy-functional monomeric (meth) acrylic component, such as glycidyl acrylate, glycidyl methacrylate, or a combination thereof, preferably in that the polyepoxide modifier is a copolymer which includes the epoxy-functional (meth) acrylic acid monomeric component and an additional monomeric component, preferably wherein the additional monomeric component includes an α-olefin monomer, preferably wherein the copolymer also comprises a monomeric (meth) acrylic component which lacks an epoxy group.
[0003]
3. Method according to claim 1 or 2, characterized by the fact that the polyepoxide modifier is poly (ethylene-methyl co-acrylate-glycidyl cometacrylate).
[0004]
4. Method according to any one of the preceding claims, characterized by the fact that the polyepoxide modifier has an average numerical molecular weight of 15,000 to 150,000 grams per mol, and / or in which the polyepoxide modifier has an equivalent weight of epoxy from 200 to 10,000 grams per mol.
[0005]
Method according to any one of the preceding claims, characterized in that the poly (lactic acid) constitutes 70% by weight or more of the thermoplastic composition.
[0006]
6. Method according to any one of the preceding claims, characterized by the fact that the melt combination occurs at a temperature of 180 ° C to 220 ° C and the extrusion of the thermoplastic composition occurs at a temperature of 235 ° C to 300 ° C.
[0007]
Method according to any one of the preceding claims, characterized by the fact that the thermoplastic composition has a glass transition temperature of 55 ° C to 65 ° C.
[0008]
Method according to any one of the preceding claims, characterized in that the fused combined composition comprises a plurality of discrete domains dispersed in a continuous phase, the discrete domains containing the polyepoxide modifier and the continuous phase containing poly (acid lactic acid), preferably where the domains are 10 to 1,000 nanometers in size.
[0009]
9. Method according to any one of the preceding claims, characterized in that the moisture content of the poly (lactic acid) before the melt combination is 1 to 100 parts per million and the moisture content of the thermoplastic composition before of the extrusion is from 100 to 500 ppm.
[0010]
10. Poly (lactic acid) fiber, characterized in that it is formed by the method as defined in any of the preceding claims.
[0011]
11. Poly (lactic acid) fiber having an average diameter of 5 to 25 micrometers, the fiber comprising a thermoplastic composition formed by the reaction of the poly (lactic acid) with a polyepoxide modifier, in which the polyepoxide modifier includes a copolymer that contains an epoxy modified monomeric (meth) acrylic component and an olefin monomeric component, where the fiber has a glass transition temperature of 55 ° C to 65 ° C, and exhibits a peak elongation of 50% or more and a toughness of 7.35 to 58.84 mN per denier (0.75 to 6 grams-force per denier); characterized by the fact that the thermoplastic composition further comprises a polymeric stiffening additive, wherein the polymeric stiffening additive is a polyolefin.
[0012]
12. Poly (lactic acid) fiber according to claim 10 or 11, characterized by the fact that the fiber exhibits a peak elongation of 100% to 350% and a toughness of 14.71 to 34.32 mN per DENIER (1.5 to 3.5 grams-force per denier).
[0013]
13. Poly (lactic acid) fiber according to any one of claims 10 to 12, characterized by the fact that the thermoplastic composition comprises a plurality of discrete domains dispersed in a continuous phase, the discrete domains containing the polyepoxide modifier and the continuous phase containing poly (lactic acid).
[0014]
14. Non-woven weave, characterized in that it comprises the fiber as defined in any one of claims 10 to 13.

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CN104841203B|2015-06-05|2017-01-25|南通大学|Nano-montmorillonite/polylactic acid melt-blown filtering material|

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KR20190029720A|2016-08-11|2019-03-20|킴벌리-클라크 월드와이드, 인크.|Reinforced thermoplastic polyolefin elastomer film|

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CN107653514B|2017-09-26|2020-06-09|江南大学|Skin-core structure composite fiber and high-performance fiber-based composite board|

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法律状态:
2019-04-30| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-12-31| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-06-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-10-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-10| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|

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2020-12-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/07/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/856,012|US8936740B2|2010-08-13|2010-08-13|Modified polylactic acid fibers|

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US12/856,012|2010-08-13|

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PCT/IB2011/053009|WO2012020335A2|2010-08-13|2011-07-06|Modified polylactic acid fibers|

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