FILM UNDERSTANDING A THERMOPLASTIC COMPOSITION, AND, ARTICLEABSORVENT

专利摘要:
RENEWABLE POLYESTER FILM WITH LOW MODULE AND HIGH STRETCH BY TENSION Presentation of a film formed from a thermoplastic compound. The thermoplastic compound containing a renewable rigid polyester and a polymeric hardening additive. The curing additive can be dispersed as physical domains within a continuous matrix of the renewable polyester. An increase in the deformation force and the elongation stress causes the decomposition of the renewable polyester matrix in the areas located adjacent to the discrete domains. This can result in the formation of several empty areas adjacent to the discrete domains, which can help to dissipate the energy under load and increase the strain elongation. To further increase the dissipation capacity of this form of film energy, these inventors have discovered that an interphasic modifier can be employed that reduces the degree of friction between the hardening additive and the renewable polyester, thus reducing the hardness (tension module) of the film.
公开号:BR112014019496B1
申请号:R112014019496-3
申请日:2013-01-28
公开日:2021-02-23
发明作者:Vasily A. Topolkaraev；Ryan J. Mceneany；Neil T. Scholl；Tom Eby
申请人:Kimberly-Clark Worldwide, Inc；
IPC主号:

专利说明:

Background of the invention
[001] Films are used in a wide variety of applications, including as packaged items (such as food) or in absorbent personal hygiene items (such as diapers, feminine hygiene items, etc.). A problem associated with many conventional films is that they are often formed from a synthetic polymer (for example, LLDPE) that is non-renewable. Unfortunately, the use of renewable polymers in such films is problematic due to the difficulty involved with the thermal processing of these polymers. Renewable polyesters, for example, have a relatively high glass transition temperature and usually demonstrate high rigidity and modulus of elasticity, with low ductility / elongation at break. As an example, polylactic acid has a glass transition temperature of about 59 ° C and an elastic modulus of about 2 GPa or more. However, the stress elongation (at break) for PLA materials is only about 5%. Such a high modulus and low elongation significantly limits the use of such polymers in films, in which a good balance between stiffness and elongation of the material is required. In addition to these problems, polylactic acid, for example, is also very rigid for flexible film applications and tends to have performance problems during use, such as causing noise in feminine hygiene products.
[002] Thus, there is currently a need for a film to be formed from a renewable polyester and still be able to have a relatively low modulus and a high tensile elongation. Summary of the invention
[003] In accordance with an embodiment of the present invention, a film comprising a thermoplastic composition is disclosed. The thermoplastic composition comprises at least one rigid renewable polyester having a glass transition temperature of about 0 ° C or more, about 1% to 30% by weight of at least one polymeric curing additive based on the weight of the polyester renewable, and from about 0.1% to 20% by weight of at least one interphase modifier based on the weight of the renewable polyester. The thermoplastic composition has a morphology in which a plurality of separate primary domains is dispersed within a continuous phase, the domains containing the polymeric curing additive and the continuous phase containing the renewable polyester. The film also has an elasticity modulus in the longitudinal and transverse direction of the machine of about 2,500 megapascals or less, a tensile elongation at break in the longitudinal direction of about 10% or more, and a tensile elongation at break in the transversal machine direction of about 15% or more, in which the modulus of elasticity and the elongation at break are determined at 23 ° C, according to the ASTM D638-10 standard. In addition, the ratio of the glass transition temperature of the thermoplastic composition to the glass transition temperature of the renewable polyester is about 0.7 to 1.3.
[004] According to another embodiment of the present invention, a film comprising a thermoplastic composition is disclosed having a thickness of 1 to 200 micrometers and comprises a thermoplastic composition. The thermoplastic composition comprises about 70% by weight or more than at least one polylactic acid having a glass transition temperature of about 0 ° C or more, from about 0.1% to 30% by weight of at least one polymeric curing additive, and from about 0.1% to 20% by weight of at least one interphase modifier. The film has an elasticity modulus in the longitudinal and transverse direction of the machine of about 2,500 megapascals or less, an elongation at break in the longitudinal direction of about 10% or more, and an elongation at break in the direction cross-section of the machine of about 15% or more, where the modulus of elasticity and elongation at break are determined at 23 ° C, according to the ASTM D638-10 standard.
[005] In accordance with yet another embodiment of the present invention, an absorbent article which is disclosed comprises a liquid impermeable layer in general, comprising a film, as described herein.
[006] Other features and aspects of the present invention are discussed in more detail below. Brief description of the illustrations
[007] The complete and enabling disclosure of the present invention, including the best mode, directed to an expert in the art, is defined more particularly in the rest of the specification, which makes reference to the attached figures in which:
[008] Fig. 1 is a schematic illustration of an embodiment of a method for forming the film of the present invention;
[009] Fig. 2 is a photomicrograph of SEM (scanning electron microscope) of a sample from Example 3, before applying an external force; and
[0010] Fig. 3 is a SEM photomicrograph of a sample from Example 3, after applying an external force.
[0011] The repeated use of reference characters of the present specification and the drawings are intended to represent the same or similar characteristics or elements of the invention. Detailed Description of Representative Forms of Realization
[0012] Detailed references will be made to various configurations of the invention, with one or more examples described below. Each example is provided for the purpose of explanation, not limitation. Indeed, 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 scope or spirit of the invention. For example, the features illustrated or described as part of a configuration can be used in another configuration, to obtain a third configuration. Thus, it is intended that the present invention encompasses those modifications and variations that are within the scope of the appended claims and their equivalents.
[0013] In general, the present invention is directed to a film that is formed from a thermoplastic compound. The thermoplastic compound containing a renewable rigid polyester and a polymeric hardening additive. The present inventors have found that the specific nature of the components can be carefully controlled to achieve a composition with the desired morphological characteristics. More particularly, the curing additive can be dispersed as separate physical domains within a continuous matrix of the renewable polyester. During the initial application of an external force in low elongation strain, the composition can behave as a monolithic material that has high rigidity and tensile modulus. However, an increase in the deformation force and elongation stress causes detachment in the renewable polyester matrix in those areas located adjacent to the separate domains. This can result in the formation of several empty areas adjacent to the discrete domains, which can help to dissipate the energy under load and increase the strain elongation. To further increase the film's ability to dissipate energy in this way, the present inventors have found that an interphasic modifier can be used, which reduces the degree of connectivity and friction between the curing additive and the renewable polyester and therefore reduces the stiffness (tension module) of the film. The reduced connectivity and friction between the polymers also increases the degree and uniformity of the detachment, which can help to distribute the resulting voids in a substantially homogeneous way through the composition. For example, empty spaces can be distributed in columns that are oriented in a direction usually perpendicular to the direction in which a tension is applied. Without intending to be limited by theory, it is believed that the presence of a homogeneously distributed void system can result in a significant energy dissipation under load and, thus, a significantly improved elongation.
[0014] Various embodiments of the present invention will now be described in more detail. I. Thermoplastic compound A. Renewable polyester
[0015] Renewable polyesters typically comprise about 70% to 99% by weight, in some embodiments about 75% to 98% by weight and in some embodiments, from about 80% to 95% by weight of the thermoplastic compound. Any of a variety of renewable polyesters can generally be used in the thermoplastic composition, such as aliphatic polyesters, such as polycaprolactone, polyesteramides, polylactic acid (PLA) and its copolymers, polyglycolic acid, polyalkylene carbonates (for example, carbonate carbonate) polyethylene), poly-3-hydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxybutyrate-co-4-hydroxybutyrate, copolymers of poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), poly-3-hydroxybutyrate-co-3-hydroxyhexanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxydecanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate and aliphatic polymers succinate based (for example, polybutylene succinate, polybutylene succinate adipate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (for example, polybutylene adipate terephthalate, polyethylene terephthalate adipate, polyethylene adipate isophthalate, polybutylene adipate isophthalate, etc.); aromatic polyesters (for example, polyethylene terephthalate, polybutylene terephthalate, etc.); and so on.
[0016] Normally, the thermoplastic compound contains at least one renewable polyester which is rigid in nature and therefore has a relatively high glass transition temperature. For example, the glass transition temperature ("Tg") can be about 0 ° C or more, in some embodiments from about 5 ° C to 100 ° C, in some embodiments about 30 ° C to 80 ° C, and in some embodiments, from about 50 ° C to 75 ° C. Renewable polyester can also have a melting temperature of about 140 ° C to 260 ° C, in some embodiments from about 150 ° C to about 250 ° C, and in some embodiments, from about from 160 ° C to 220 ° C. The melting temperature can be determined using differential scanning calorimetry (“DSC”), in accordance with the ASTM D-3417 standard. The glass transition temperature can be determined by means of dynamic-mechanical analysis, according to the ASTM E1640-09 standard.
[0017] A particularly suitable rigid polyester is polylactic acid, which can generally be derived from monomer units of any isomer of lactic acid, such as levogiro-lactic acid (“L-lactic acid”), dextrogiro-lactic acid (“ D-lactic acid ”), meso-lactic acid or mixtures thereof. Monomer units can also be formed from anhydrides of any lactic acid isomer, including L-latid, D-latid, meso-latid or mixtures thereof. Cyclic dimers of such lactic acids and / or latids 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. Polylactic acid can be a homopolymer or a copolymer, such as one that contains monomer units derived from L-lactic acids and monomer units derived from D-lactic acid. Although not required, the content rate of a 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. Various polylactic acids, each having a different ratio between the monomer unit derived from L-lactic acid and the monomer unit derived from D-lactic acid, can be mixed in an arbitrary proportion. Of course, polylactic acid can also be mixed with other types of polymers (for example, polyolefins, polyesters, etc.).
[0018] In a particular embodiment, polylactic acid has the following general structure:

[0019] A specific example of a suitable polylactic acid polymer that can be used in the present invention is commercially available from Biomer, Inc. of Krailling, Germany under the name Biomer L9000 ™. Other suitable polylactic acid polymers are commercially available from NatureWorks LLC of Minnetonka, Minnesota (NatureWorks®) or Mitsui Chemical (LACEA ™). Still other suitable polylactic acids can be described in U.S. Patent No. 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 for reference for all purposes.
[0020] Polylactic acid typically has a number average molecular weight ("Mn") ranging from about 40,000 to 160,000 grams per mole, in some embodiments from about 50,000 to 140,000 grams per mole, and in some embodiments, from about 80,000 to 120,000 grams per mol. Likewise, the polymer also typically has an average molecular weight ("Mw") ranging from about 80,000 to 200,000 grams per mole, in some embodiments from about 100,000 to 180,000 grams per mole, and in some embodiments, from about 110,000 to 160,000 grams per mol. The ratio of the average molecular weight by weight to the average molecular weight in number ("M w / Mn"), that is, the "polydispersity index", is also relatively low. For example, the polydispersity index typically ranges from about 1.0 to 3.0, in some embodiments from about 1.1 to 2.0, and in some embodiments, from about 1, 2 to 1.8. The weight and average molecular weight numbers of the weight can be determined by methods known to those skilled in the art.
[0021] Polylactic acid can also have an apparent viscosity of about 50 to 600 Pascal-seconds (Pa-s), in some embodiments of about 100 to 500 Pa-s, and in some embodiments, the from about 200 to 400 Pa-s, as determined at a temperature of 190 ° C and a shear rate of 1000 sec.-1. The melt flow rate of polylactic acid (on a dry basis) can also vary from about 0.1 to about 40 grams for 10 minutes, in some embodiments from about 0.5 to 20 grams for 10 minutes, and in some embodiments, from about 5 to 15 grams for 10 minutes, determined at a load of 2,160 grams and at 190 ° C.
[0022] Some types of pure polyesters (for example, polylactic acid) can absorb water from the environment, so that it has a content of about 500 to 600 parts per million ("ppm"), or even greater than moisture, based on the dry weight of the polylactic acid. The moisture content can be determined in a variety of ways as is known in the art, as in accordance with ASTM D 7191-05, as described below. Due to the presence of water during the melting process, it is possible to hydrolytically degrade the polyester and reduce its molecular weight, it is sometimes desirable to dry the polyester before mixing. In most embodiments, for example, it is desired that the renewable polyester has a content of about 300 parts per million ("ppm") of moisture or less, in some embodiments about 200 ppm or less, in some embodiments of about 1 to 100 ppm before mixing with the curing additive. Drying of the polyester can occur, for example, at a temperature of about 50 ° C to 100 ° C, and in some embodiments, from about 70 ° C to 80 ° C. B. Polymeric curing additive
[0023] As indicated above, the thermoplastic compound of the present invention also contains a polymeric curing additive. Due to its polymeric nature, the curing additive has a relatively high molecular weight, which can help to improve melt strength and stability of the thermoplastic composition. Although not required, the polymeric curing additive can generally be immiscible with renewable polyester. In this way, the curing additive can be better dispersed as distinct phase domains within a continuous phase of the renewable polyester. The distinct domains are able to absorb the energy that arises from an external force, which increases the overall strength and strength of the resulting material. Domains can have a variety of different shapes, such as elliptical, spherical, cylindrical, etc. In one embodiment, for example, the domains are substantially elliptical in shape. The physical dimension of an individual domain is generally small enough to minimize the spread of cracks through the polymer material by applying an external stress, but large enough to initiate microscopic plastic deformation and allow for shear zones around inclusions of particles.
[0024] While polymers may be immiscible, the curing additive, however, can be selected to have a solubility parameter that is relatively similar to that of renewable polyester. This can improve the interfacial compatibility and physical interaction of the boundaries of the distinct and continuous phases, and thus reduce the likelihood of fracturing the composition. In this regard, the ratio of the solubility parameter for the renewable polyester to the curing additive is typically about 0.5 to about 1.5, and in some embodiments, from about 0.8 to 1.2. For example, the polymeric curing additive may have a solubility parameter of about 15 to about 30 MJoules 1/2 / M3 / 2, and in some embodiments, from about 18 to 22 MJoules 1/2 / M3 / 2, while polylactic acid may have a solubility parameter of about 20.5 MJoules 1/2 / M3 / 2. The term "solubility parameter" as used herein refers to the "Hildebrand solubility parameter", which is the square root of the cohesive energy density and calculated according to the following equation:
where: Δ H v = heat of vaporization R = ideal constant gas T = temperature Vm = Molecular volume
[0025] Hildebrand solubility parameters for many polymers are also available in the Solubility Handbook of Plastics, by Wyeych (2004), which is incorporated by reference.
[0026] The polymeric curing additive can also have a certain melt flow rate (or viscosity) to ensure that the resulting distinct and void domains can be maintained properly. For example, if the melting flow rate of the curing additive is too high, it tends to flow and disperse uncontrollably through the continuous phase. This results in lamellar or laminar domains that are difficult to maintain and are also likely to fracture prematurely. On the other hand, if the melting flow rate of the curing additive is very low, it tends to agglutinate and form large elliptical domains, which are difficult to disperse during mixing. This can cause irregular distribution of the curing additive throughout the continuous phase. In this regard, the present inventors have found that the ratio of the melt flow rate of the curing additive to the melt flow rate of the renewable polyester is typically about 0.2 to 8, in some embodiments of about 0.5 to 6, and in some embodiments, from about 1 to 5. The polymeric curing additive can, for example, have a melt flow rate of about 0.1 to about 250 grams per 10 minutes, in some embodiments of about 0.5 to 200 grams for 10 minutes, and in some embodiments, from about 5 to 150 grams for 10 minutes, determined at a load of 2,160 grams and 190 ° C.
[0027] In addition to the properties indicated above, the mechanical characteristics of the polymeric curing additive can also be selected to achieve the desired increase in strength. For example, when a mixture of renewable polyester and hardening additive is applied with an external force, shear and / or areas of plastic flow may occur in and around the domains of different phases, as a result of stress concentrations arising from a difference in the modulus of elasticity of the curing additive and renewable polyester. Higher concentrations of stresses promote the most intense plastic flow in the domains, which allows them to become significantly stretched when the stresses are transmitted. These elongated domains allow the composition to exhibit a more flexible and softer behavior than rigid polyester resin. To increase stress concentrations, the curing additive is selected to have a Young modulus of relatively low elasticity compared to renewable polyester. For example, the ratio of the elastic modulus of the renewable polyester to that of the curing 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 curing additive can, for example, vary from about 2 MPa to about 500 megapascals (MPa), in some embodiments of about 5 MPa at about 300 MPa, and in some embodiments, from about 10 MPa to about 200 MPa. In contrast, the modulus of elasticity of polylactic acid is typically about 800 MPa to 2,000 MPa.
[0028] In order to transmit the desired increase in hardening, the polymeric hardening additive can also exhibit an elongation at break (i.e., the percentage of elongation of the polymer at its yield limit) greater than renewable polyester. For example, the polymeric curing additive of the present invention may exhibit an elongation at break of about 50% or more, in some embodiments of about 100% or more, in some embodiments of about 100% to about 2,000%, and in some embodiments, from about 250% to about 1,500%.
[0029] While a wide variety of polymeric additives with the properties identified above can be used, particularly suitable examples of such polymers can include, for example, polyolefins (for example, polyethylene, polypropylene, polybutylene, etc.); styrene copolymers (for example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-butadiene-styrene, etc.); polytetrafluoroethylenes; polyesters (for example, recycled polyester, polyethylene terephthalate, etc.); polyvinyl acetates (for example, poly (ethylene vinyl acetate), polyvinyl chloride acetate, etc.); polyvinyl alcohols (eg polyvinyl alcohol, poly (ethylene vinyl alcohol), etc.; polyvinyl butyrals, acrylic resins (eg polyacrylate, polymethylacrylate, polymethylmethacrylate, etc.); polyamides (eg nylon); polyvinyl chlorides ; polyvinyl chlorides; polystyrenes, polyurethanes, etc. Suitable polyolefins may, for example, include ethylene polymers (for example, low density polyethylene ("LDPE"), high density polyethylene ("HDPE"), linear polyethylene of low density ("LLDPE"), etc.), propylene homopolymers (for example, syndiotactic, atactic, isotactic, etc.), propylene copolymers, and so on.
[0030] In a particular embodiment, the polymer is propylene, such as homopolypropylene or a propylene copolymer. The propylene polymer can, for example, be formed from a substantially isotactic polypropylene homopolymer or a copolymer with a content equal to or less than about 10% by weight of another monomer, that is, at least about 90% by weight propylene. Such homopolymers can have a melting point of about 160 ° C to 170 ° C.
[0031] In yet another embodiment, the polyolefin can be a copolymer of ethylene or propylene with another α-olefin, such as a C3-C20 α-olefin or C3-C12 α-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 methyls, ethyl or propyl substitutes; 1-hexene with one or more methyls, ethyl or propyl substitutes; 1-heptene, with one or more methyls, ethyl or propyl substitutes; 1-octene, with one or more methyls, ethyl or propyl substitutes; 1-nonene, with one or more methyls, ethyl or propyl substitutes; 1- decene with ethyl, methyl or dimethyl substitutes; 1-dodecene; and styrene. The particularly desired α-olefin comonomers are 1-butene, 1-hexene and 1-octene. The ethylene and propylene content of these copolymers can vary from 60% to 99% mol, in some embodiments from 80% to 98.5 mol%, and in some embodiments, from 87% to 97.5 mol%. The content of α-olefin can vary from about 1% to 40 mol%, in some embodiments from about 1.5% to 15 mol%, and in some embodiments, from about 2.5 % to 13 mol%
Exemplary olefin copolymers for use in the present invention include ethylene-based copolymers, available under the name EXACT ™ from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are available under the name ENGAGE ™, AFFINITY ™, DOWLEX ™ (LLDPE) and ATTANE ™ (ULDPE) from Dow Chemical Company of Midland, Michigan. Other suitable ethylene polymers are described in U.S. Patent No. 4,937,299 to Ewen et al .; 5,218,071 to Tsutsui et al .; 5,272,236 to Lai et al .; and 5,278,272 for Lai et al., which are incorporated herein in their entirety for reference for all purposes. Suitable propylene copolymers are also commercially available under the Vistamaxx ™ designations of ExxonMobil Chemical Co. of Houston, Texas; FINA ™ (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMER ™ made available by Mitsui Petrochemical Industries; and VERSIFY ™ available from Dow Chemical Co. of Midland, Michigan. Other examples of suitable propylene polymers are described in U.S. Patent No. 6,500,563 to Datta et al .; 5,539,056 to Yang et al .; and 5,596,052 to Resconi et al., which are incorporated herein in their entirety for reference purposes.
[0033] Any of a variety of known techniques can generally be used 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 within a molecular chain and uniformly distributed among the different molecular weight fractions. Metallocene-catalyzed polyolefins are described, for example, in U.S. Patent No. 5,571,619 to McAlpin et al .; 5,322,728 for Davis et al .; 5,472,775 to Obijeski et al .; 5,272,236 to Lai et al .; and 6,090,325 for Trigo et al., which are incorporated herein in their entirety for reference for all purposes. Examples of metallocene catalysts include bis (n-butylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, scandium bis (cyclopentadienyl) chloride, bis (indenyl) zirconium dichloride, methyl (dichloro) dichloride bis (methylcyclopentadienyl) dichloride, zirconium, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafniocene dichloride, isopropyl dichloride (cyclopentadienyl, -1- flourenyl), zirconium, molybocene, dichloride, dichloride, dichloride, dichloride, nickel zirconocene chloride, 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) less than 4, controlled short chain branch distribution, and controlled isotacticity.
[0034] Regardless of the materials used, the relative percentage of the polymeric curing additive in the thermoplastic composition is selected to achieve the desired properties without significantly impacting the ability to renew the resulting composition. For example, the curing additive is typically used in an amount of about 1% to 30% by weight, in some embodiments from about 2% to 25% by weight, and in some embodiments, from about from 5% to 20% by weight of the thermoplastic composition, based on the weight of the renewable polyesters employed in the composition. The concentration of the curing additive in the entire thermoplastic composition can also be from about 0.1% to 30% by weight, in some embodiments from about 0.5% to 25% by weight and in some forms from about 1% to 20% by weight. C. Interphase modifier
[0035] An interphase modifier is also used in the thermoplastic composition to modify the interaction between the hardening additive and the renewable polyester matrix. The modifier, in general, has a liquid or semi-solid form at room temperature (for example, 25 ° C), so that it has a relatively low viscosity, which allows it to be more easily incorporated into the thermoplastic composition and easily migrate to the polymer surfaces. In this regard, the kinematic viscosity of the interphase modifier is typically about 0.7 to about 200 centistokes ("CS"), in some embodiments from about 1 dog to about 100 dog, and in some ways embodiment, from about 1.5 dogs to about 80 dogs, determined at 40 ° C. In addition, the interphase modifier is also typically hydrophobic so that it has an affinity for the polymer curing additive, which results in a change in the interfacial tension between the polyester and the renewable curing additive. By reducing the physical forces at the interfaces between the polyester and the curing additive, it is believed that the low viscosity, the hydrophobic nature of the modifying agent can help facilitate displacement from the polyester matrix by applying an external force. As used herein, the term "hydrophobic" typically refers to a material that has a water-to-air contact angle of about 40 ° or more, and in some cases, about 60 ° or more. In contrast, the term "hydrophilic" typically refers to a material that has a water-to-air contact angle of less than about 40 °. A suitable test to measure the contact angle is the ASTM D5725-99 (2008).
Suitable hydrophobic and low viscosity interphasic modifiers may include, for example, silicones, silicone polyether copolymers, aliphatic polyesters, aromatic polyesters, alkylene glycols (e.g. ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene) glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.), alkanedioles (eg 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl- 1,3- cyclobutanediol, etc.), amine oxides (e.g., octyldimethylamine oxide), fatty acid esters, etc. A particularly suitable interphase modifier is polyether polyol, available under the trade name Pluriol® from BASF Corp WI. Another suitable modifier is a partial renewable ester, commercially available under the name HALLGREEN® IM from HALLSTAR.
[0037] Although the actual amount may vary, the interphase modifier is typically used in an amount of about 0.1 to 20% by weight, in some embodiments from about 0.5% to 15% by weight, and in some embodiments, from about 1% to 10% by weight of the thermoplastic composition, based on the weight of the renewable polyesters employed in the composition. The concentration of the interphase modifier in the entire thermoplastic composition can also be from about 0.05% to 20% by weight, in some embodiments from about 0.1% to 15% by weight and in some forms from about 0.5% to 10% by weight.
[0038] When used in the amounts mentioned above, the interphase modifier has a property that allows it to easily migrate to the interfacial surface of polymers and facilitate displacement, without disturbing the general melting properties of the thermoplastic composition. For example, the interphase modifier does not normally have a plasticizing effect on the polymer by reducing its glass transition temperature. Quite the contrary, the present inventors have found that the glass transition temperature of the thermoplastic composition can be substantially the same as that of the initial renewable polyester. In this respect, the ratio of the temperature of the glass in the composition to that of the polyester is normally from about 0.7 to about 1.3, in some embodiments from about 0.8 to about 1, 2, and in some embodiments, from about 0.9 to about 1.1. The thermoplastic composition can, for example, have a glass transition temperature of between about 35 ° C to 80 ° C, in some embodiments from about 40 ° C to 80 ° C, and in some embodiments, from about 50 ° C to 65 ° C. The melt flow rate of the thermoplastic composition can also be similar to that of renewable polyester. For example, the melt flow rate of the composition (on a dry basis) can also vary from about 0.1 to 70 grams for 10 minutes, in some embodiments from about 0.5 to 50 grams for 10 minutes, and in some embodiments, from about 5 to 25 grams for 10 minutes, determined at a load of 2,160 grams and at a temperature of 190 ° C. D. Compatibilizer
[0039] As indicated above, the polymeric curing additive is generally selected so that it has a solubility parameter relatively close to that of renewable polyester. Among other things, this can increase the degree of phase compatibility and improve the overall distribution of the distinct domains within the continuous phase. However, in certain embodiments, a compatibilizer can optionally be employed to further increase the degree of compatibility between the renewable polyester and the polymeric curing additive. This may be particularly desirable when the polymeric curing additive has a polar part, such as polyurethanes, acrylic resins, etc. When used, compatibilizing agents typically make up from about 0.5% to 20% by weight, in some embodiments from about 1% to 15% by weight, and in some embodiments, from about from 1.5% to 10% by weight of the thermoplastic composition. An example of a suitable compatibilizing agent is a functionalized polyolefin. The polar component can, for example, be provided by one or more functional groups and the non-polar component can be provided by an olefin. The olefin component of the compatibilizer can generally be formed from any straight or branched chain of α-olefin monomer, oligomer or polymer (including copolymers) derived from an olefin monomer, as described above.
[0040] The functional group of the compatibilizing agent can be any group that provides a polar segment for the molecule. Particularly suitable functional groups are maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, a product of the maleic anhydride and diamine reaction, methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, etc. Modified maleic anhydride polyolefins are particularly suitable for use in the present invention. Such modified polyolefins are typically formed by grafting maleic anhydride onto a material of polymeric structure. Such maleate polyolefins are available from EI du Pont de Nemours and Company under the name Fusabond®, such as that of the P series (chemically modified polypropylene), E series (chemically modified polyethylene), C series (chemically modified ethylene vinyl acetate), series A (chemically modified or chemically modified ethylene acrylate copolymers or terpolymers), or N series (chemically modified ethylene-propylene, ethylene-propylene-diene monomer ("EPDM") or ethylene-octene). Alternatively, maleatated polyolefins are also available from Chemtura Corp under the name Polybond® and from the Eastman Chemical Company under the name Eastman G series.
[0041] In certain embodiments, the compatibilizing agent can also be reactive. An example of a reactive compatibilizing agent is a polyepoxide modifier that contains, on average, at least two oxirane rings per molecule. Without intending to be limited by theory, it is believed that such polyepoxide molecules can induce the reaction of renewable polyester under certain conditions, thus improving its resistance to melting, without significantly reducing the glass transition temperature. The reaction may involve chain extension, side chain branching, grafting, copolymer formation, etc. Chain extension, for example, can occur through a variety of different reaction pathways. For example, the modifier may allow a ring-opening nucleophilic reaction through a renewable polyester carboxyl end group (esterification) or through a hydroxyl group (etherification). Side reactions of oxazoline can occur to form parts of stearide. Through such reactions, the molecular weight of the renewable polyester can be increased to compensate for the degradation observed frequently during the casting process. While it is desirable to induce a reaction with the renewable polyester, as described above, the present inventors have found that an excess of a reaction can lead to crosslinking between the polyester backbones. If crosslinking is allowed to proceed significantly, the resulting polymer mixture can become brittle and difficult to form a film with the desired properties of modulus of elasticity and elongation.
[0042] In this regard, the present inventors have found that polyepoxide modifiers with relatively low epoxy functionality are particularly effective, which can be quantified by their "epoxy equivalent weight." The epoxy equivalent weight reflects the amount of resin that contains a molecule in an epoxy group, and can be calculated by dividing the number of average molecular weight of the modifying agent by the number of epoxy groups in the molecule. The polyepoxide modifier of the present invention typically has a number average molecular weight of about 7,500 g / mol to 250,000 grams per mol, in some embodiments from about 15,000 g / mol to 150,000 grams per mol, and in some forms of embodiment, from about 20,000 g / mol to 100,000 grams per mol, 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, 15 to 40 epoxy groups. In turn, the epoxy equivalent weight can be less than about 15,000 grams per mol, in some embodiments from about 200 g / mol to about 10,000 grams per mol, and in some embodiments, from about 500 g / mol to about 7,000 grams per mol.
[0043] The polyepoxide can be a straight or branched chain, homopolymer or copolymer (for example, random, graft, block, etc.). containing epoxy terminal groups, oxirane structural units and / or epoxy pendant groups. The monomers used to form these polyepoxides can vary. In a particular embodiment, for example, the polyepoxide modifier contains at least one monomeric (meth) acrylic component functional with epoxy. As used herein, the term "(meth) acrylic" includes acrylic and methacrylic monomers, as well as their salts or esters, such as acrylate and methacrylate monomers. For example, the appropriate 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 allylglycidyl ether, glycidyl ethacrylate and glycidyl itoconate.
[0044] Polyepoxide typically has a relatively high molecular weight, as indicated above, so that it can not only result in the extension of the renewable polyester chain, but also helps to achieve the desired blend morphology. Thus, the resulting melt flow rate of the polymer ranges from about 10 g to about 200 grams for 10 minutes, in some embodiments from about 40 g to 150 grams for 10 minutes, and in some embodiments of about 60 g to 120 grams for 10 minutes, determined at a load of 2,160 grams and at a temperature of 190 ° C.
[0045] If desired, additional monomers can also be employed in the polyepoxide to help achieve the desired molecular weight. Such monomers can vary and include, for example, ester monomers, (meth) acrylic monomers, olefinic monomers, amide monomers, etc. In a particular embodiment, for example, the polyepoxide modifier includes at least one linear or branched monomeric α-olefin chain, 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; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substitutes; 1-hexene with one or more methyl, ethyl or propyl substitutes; 1-heptene with one or more methyl, ethyl or propyl substitutes; 1- octene with one or more methyl, ethyl or propyl substitutes; 1-nonene with one or more methyl, ethyl or propyl substitutes; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. Particularly desired α-olefin comonomers are ethylene and propylene.
[0046] Another suitable monomer may include a (meth) acrylic monomer that is not functional with epoxy. Examples of (meth) acrylic monomers can include methyl acrylate, ethyl acrylate, n-propyl, i-propyl acrylate, n-butyl, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate , cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl, n-butyl methacrylate, i-propyl methacrylate, i-butyl methacrylate, n-amyl, methacrylate n-hexyl, i-amyl methacrylate, s-butyl-methacrylate, t-butyl, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinamyl, crotyl methacrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, 2-ethyl methacrylate, cyclopentyl methacrylate, isobornyl methacrylate, etc., as well as their combinations.
[0047] In a particularly desirable embodiment of the present invention, the polyepoxide modifier is a terpolymer formed from a monomeric (meth) acrylic component, monomeric α-olefin component and non-epoxy functional monomeric (meth) acrylic component. For example, the polyepoxide modifier can be poly (ethylene-co-methacrylate-co-glycidyl methacrylate), which has the following structure:
where, x, y and z are 1 or greater.
[0048] The functional epoxy monomer can be formed into a polymer, using a variety of known techniques. For example, a monomer that contains polar functional groups can be grafted onto a polymer 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 for reference purposes. In other embodiments, a monomer containing epoxy functional groups can be copolymerized with a monomer to form a random block or copolymer, using known free radical polymerization techniques, such as high pressure reactions, Ziegler catalyst reaction systems -Natta, single site catalyst (eg metallocene) reaction systems, etc.
[0049] The relative part of the monomeric component can be selected to achieve a balance between epoxy reactivity and melt flow rate. More particularly, the high content of epoxy monomers can result in good reactivity with renewable polyester, but the high concentration of one content can reduce the melt flow rate so that the polyepoxide modifier negatively impacts the strength of the polymer mixture. . Thus, in most embodiments, epoxy functional (meth) acrylic monomers make up from about 1% to 25% by weight, in some embodiments from about 2% to 20% by weight, and in some forms from about 4% to 15% by weight of the copolymer. A-olefin monomers can also comprise from about 55% to 95% by weight, in some embodiments from about 60% to 90% by weight and in some embodiments, from about 65% to 85% by weight. When used, the other monomeric components (for example, non-epoxy functional (meth) acrylic monomers) can comprise from about 5% to 35% by weight, in some embodiments from about 8% to 30% by weight, and in some embodiments, from about 10% to 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 or AX8900. LOTADER® AX8950, for example, 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 monomer content of methyl acrylate of 13% to 17% by weight, and an ethylene monomer content of 72% to 80% by weight.
[0050] In addition to controlling the type and relative quantity of monomers used to form the polyepoxide modifier, the percentage of total weight can also be controlled to achieve the desired benefits. For example, if the level of modification is very low, the desired increase in the melt and melt strength properties may not be achieved. The present inventors have also found, however, that if the level of modification is too high, the ability to form a film may be limited due to strong molecular interactions (eg, crosslinking), and the formation of a physical network by the functional groups of epoxy. Thus, the polyoxide modifier is typically used in an amount of about 0.05% to 10% by weight, in some embodiments from about 0.1% to 8% by weight, and in some embodiments, the from about 0.5% to 5% by weight and in some embodiments from 1% to 3% by weight, based on the weight of the renewable polyesters employed in the composition. The polyoxide modifier can also comprise from about 0.05% to 10% by weight, in some embodiments from about 0.05% to 8% by weight, in some embodiments from 0.1 % to 5% by weight and in some embodiments from 0.5% to 3% by weight, based on the total weight of the composition.
[0051] When used, the polyepoxide modifier can also influence the morphology of the thermoplastic composition in a way that further increases its reactivity with renewable polyester. More particularly, the resulting morphology can have a plurality of discrete domains of the polyepoxide modifier distributed through a continuous polyester matrix. The “secondary” domains can have a variety of different shapes, such as elliptical, spherical, cylindrical, etc. Regardless of the shape, however, the size of an individual secondary domain, after mixing, is small to provide a larger surface area for the reaction with the renewable polyester. For example, the size of a secondary domain (e.g., length) typically ranges from about 10 to about 1000 nanometers, in some embodiments from about 20 to about 800 nanometers, in some embodiments of about 40 to about 600 nanometers, and in some embodiments from about 50 to about 400 nanometers. As mentioned above, the curing additive also forms distinct domains within the polyester matrix, which are considered to be in the “primary” domain of the composition. Of course, it must also be understood that the domains can be formed by a combination of polyepoxide, hardening additive and / or other components of the mixture.
[0052] In addition to polyepoxides, other reactive compatibilizing agents can also be used in the present invention, such as polymers functionalized by oxazoline, polymers functionalized by cyanides, etc. When employed, such reactive compatibilizers can be used at the concentrations mentioned above for the polyepoxide modifier. In a particular embodiment, an oxazoline-grafted polyolefin can be employed which is a polyolefin grafted with an oxazoline ring-containing monomer. Oxazoline can include a 2-oxazoline, such as 2-vinyl-2-oxazoline (for example, 2-isopropenyl-2-oxazoline), 2-fatty acid-alkyl-2-oxazoline (for example, obtained from ethanolamide of oleic acid, linoleic acid, palmitoleic acid, gadoleic acid, erucic acid and / or arachidonic acid) and their combinations. In another embodiment, oxazoline can be selected from ricinoloxazoline maleinate, undecyl-2-oxazoline, soy-2-oxazoline, ricinus-2-oxazoline and combinations of these components, for example. In yet another embodiment, oxazoline is selected from 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline and combinations thereof. E. Other components
[0053] An advantageous aspect of the present invention is that good mechanical properties (for example, elongation) can be provided without the need for conventional plasticizers, such as solid or semi-solid polyethylene glycol, available from Dow Chemical under the name Carbowax ™ ). The thermoplastic composition can generally be free of such plasticizers. However, it is to be understood that plasticizers can be used in certain embodiments of the present invention. When used, however, plasticizers are typically present in an amount of less than about 10% by weight, in some embodiments from about 0.1% to 5% by weight, and in some embodiments, the from about 0.2% to 2% by weight of the thermoplastic composition. Of course, 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, solvents, solid fillers, nucleating agents (e.g., titanium dioxide, calcium carbonate, etc.). ), particulate materials and other materials added to improve the processability of the thermoplastic composition. When used, it is usually desired that the amounts of these additional ingredients are minimized to ensure optimal compatibility and economy. Thus, for example, it is usually desirable for such ingredients to be 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. II. Mix
[0054] The raw materials (for example, renewable polyester, curing additives, and interphase modifiers) can be mixed with any of a variety of known techniques. In one embodiment, for example, the raw materials can be supplied separately or in combination. For example, the raw materials can first be mixed dry to form an essentially homogeneous dry mixture. The raw materials can also be supplied, either simultaneously or in sequence to a melt processing device that is dispersedly combined with the materials. Batch and / or continuous fusion processing techniques can be used. For example, a mixer / kneader, Banbury mixer, Farrel continuous mixer, single screw extruder, double screw extruder, laminating roller, etc., can be used to mix and process the melting of the materials. Particularly suitable fusion processing devices can be a co-rotating twin screw extruder (for example, ZSK-30 extruder available from Werner & Pfleiderer Corporation, of Ramsey, New Jersey or a Thermo Prism ™ USALAB 16 extruder available from Thermo Electron Corp , Stone, England). Such extruders can include feed and purge ports and provide a high distributive intensity and dispersive mix. For example, the raw materials can be fed through the same or different feed ports of the twin screw extruder and melted to form a substantially homogeneous molten mixture. If desired, other additives can also be injected into the polymer melt and / or supplied separately in the extruder at a different point along its length. Alternatively, the additives can be pre-mixed with the renewable polyester, curing additive and / or interphase modifier.
[0055] Regardless of the specific processing technique chosen, the raw materials are mixed under sufficient shear / pressure and heat to ensure sufficient dispersion, but not so high as to adversely reduce the size of the distinct domains so that they do not are able to achieve the desired hardness and elongation. For example, mixing typically occurs at a temperature of about 180 ° C to about 260 ° C, in some embodiments of about 185 ° C to about 250 ° C, and in some embodiments, from from about 190 ° C to about 240 ° C. Similarly, the apparent shear rate during the melting process can vary from about 10 seconds-1 to about 3,000 seconds-1, in some embodiments from about 50 seconds-1 to about 2,000 seconds-1 , and in some embodiments, from about 100 seconds-1 to about 1,200 seconds-1. The apparent shear rate is equal to 4Q / πR3, where Q represents the volumetric flow rate (“m3 / s”) of the molten polymer and R is the radius ("m") of the capillary tube (for example, extrusion mold ), through which the molten polymer flows. Of course, other variables, such as residence time during fusion processing, which is inversely proportional to the throughput, can also be controlled to achieve the desired degree of homogeneity.
[0056] To achieve the desired shear conditions (eg rate, residence time, shear rate, melt processing temperature, etc.), the speed of the screw extruder can be chosen with a certain interval . Generally, an increase in the temperature of the product is observed with the increase in the speed of the thread due to the entry of additional mechanical energy into the system. For example, the thread speed can vary from about 50 rpm to about 500 revolutions per minute ("rpm"), in some embodiments from about 70 rpm to about 300 rpm, and, in some embodiments , from about 100 rpm to about 200 rpm. This can result in a temperature that is high enough to disperse the curing additive and interphase modifier without adversely affecting the size of the resulting domains. The melting shear rate, and in turn the degree to which the polymers are dispersed, can also be increased through the use of one or more distributive mixing elements and / or dispersion within the mixing section of the extruder. Distributive mixers suitable for single screw extruders may include, for example, Saxon, Dulmage, cavity transfer mixers, etc. Likewise, dispersive mixers can include the Blister ring, Leroy / Maddock mixers, CRD, etc. As is well known in the art, mixing can also be improved by using the pins in the barrel that create a folding and reorientation of the polymer melt, such as those used in Buss Kneader extrusion machines, cavity transfer mixers and mixers. vortex matching pin (Vortex Intermeshing Pin, or VIP in the acronym). III. Film construction
[0057] Any known technique can be used to form a film from the blended composition, including blowing, casting, flat extrusion, etc. In a particular embodiment, the film can be formed by a blown process in which a gas (e.g., air) is used to expand a bubble of the extruded polymer mixture through an annular mold. The bubble is then popped and collected in the form of a flat film. Processes for producing tubular films are described, for example, in U.S. Patent No. 3,354,506 to Raley; 3,650,649 for Schippers; and 3,801,429 to Schrenk et al. , as well as in US Patent Applications No. 2005/0245162 to McCormack et al. and 2003/0068951 to Boggs, et al. In yet another embodiment, however, the film is formed using a casting technique.
[0058] With reference to Fig. 1, for example, an embodiment of a method for forming a molten film is shown. In this embodiment, the raw material (not shown) is supplied to extruder 80 and then molded on a casting roll 90, to form a single layer precursor film 10a. If a multi-layer film is to be produced, the various layers are co-extruded together on the casting roll 90. The casting roll 90 can optionally be provided with embossed elements to give a pattern to the film. Normally, the casting roll 90 is maintained at a temperature sufficient to solidify and temper the plate 10a, while it is being formed, from about 20 ° C to 60 ° C. If applicable, a vacuum box can be positioned adjacent to the casting roll 90 to help keep the precursor film 10a close to the surface of the roll 90. In addition, air knives or electrostatic screens can help to force the precursor film 10a against the surface of the mold roll 90 as it moves around a spinning roll. An air knife is a device known in the art that concentrates an air flow at a high flow rate to pin the edges of the film.
[0059] Once melted, the film 10a can then optionally be oriented in one or more directions to further improve the uniformity of the film and reduce the thickness. The film can be immediately reheated to a temperature below the melting point of one or more polymers in the film, but high enough to allow the composition to be pulled or stretched. In the case of sequential orientation, the "softened" film is pulled by rollers that rotate at different speeds of rotation in such a way that the sheet is stretched to the desired stretching rate in the longitudinal direction (machine direction). This "uniaxially" oriented film can then be laminated to form a fibrous tissue. In addition, the uniaxially oriented film can also be oriented transversely to the machine to form a "biaxially oriented" film. For example, the film can be fixed on its side edges by means of chain fasteners and transported to a stretcher oven. In the stretcher oven, the film can be reheated and pulled in the machine's transverse direction to the desired stretch ratio by means of diverging chain fasteners in their forward path.
[0060] With reference again to Fig. 1, for example, a method for forming a uniaxially oriented film is shown. As illustrated, the precursor film 10a is directed to a film orientation unit 100 or machine direction guide ("MDO"), commercially available from Marshall and Willams, Co., of Providence, Rhode Island. The MDO has a plurality of drawing rollers (such as 5 to 8) that progressively stretch and thin the film in the direction of the machine, which is the direction of travel of the film, through the process, as shown in Fig. 1. Although the MDO 100 is illustrated with eight rolls, it should be understood that the number of rolls can be greater or less, depending on the level of stretching desired and the degree of stretching between each roller. The film can be stretched in single or multiple different stretch operations. It should be noted that some of the rollers in an MDO device cannot be operating at ever higher speeds. If desired, some of the MDO 100 rollers can function as preheat rollers. If present, these first rollers heat the film 10a above room temperature (for example, at 52 ° C). The progressively faster speeds of the adjacent rollers in the MDO act to stretch the film 10a. The rate at which the stretch rollers rotate determines the amount of stretch of the film and the weight of the final film.
[0061] The resulting film 10b can then be rolled up and stored on a take-up roll 60. Although not shown here, several additional possible processing and / or finishing steps known in the art, cracking, treatment, opening, graphic printing or lamination of the film with other layers (for example, non-woven fabric materials), can be carried out without departing from the spirit and scope of the invention.
[0062] The film of the present invention can be monolayer or multilayer. Multilayer films can be prepared by coextruding the layers, extrusion coating or by any conventional overlapping process. For example, the film may contain two (2) to fifteen (15) layers, and in some embodiments, from three (3) to twelve (12) layers. Such multilayer films normally contain at least one base layer and at least one additional layer (e.g., surface layer), but may contain any number of layers desired. For example, the multilayer film can be formed from a base layer and one or more surface layers, wherein the base layer is formed from the thermoplastic composition of the present invention. In most embodiments, the surface layer (s) is (are) formed from a thermoplastic composition as described above. It should be understood, however, that other polymers can also be used in the surface layers, such as polyolefin polymers (for example, linear low density polyethylene (LLDPE) or polypropylene).
The film thickness of the present invention can be relatively small, to increase flexibility. For example, the film may have a thickness of about 1 μm to 200 micrometers, in some embodiments of about 2 μm to 150 micrometers, in some embodiments of about 5 μm to 100 micrometers, and in some forms performance, from about 10 μm to 60 micrometers. Despite being so thin in thickness, the film of the present invention is nevertheless capable of maintaining good mechanical properties during use. For example, the film is relatively ductile. A parameter that is indicative of the ductility of the film is the percentage of elongation of the film at its breaking point, as determined by the strain strain curve, as obtained according to ASTM D638-10, at 23 ° C. For example, the percentage of elongation at break of the film in the machine direction ("MD") can be about 10% or more, in some embodiments about 50% or more, in some embodiments about 80 % or more, and in some embodiments, from about 100% to about 600%. Likewise, the percentage of elongation at break of the film in the transverse direction of the machine ("CD") can be about 15% or more, in some embodiments about 40% or more, in some embodiments about 70% or more, and in some embodiments, from about 100% to about 400%. Another parameter that is indicative of ductility is the modulus of elasticity of the film, which is equal to the ratio of the tensile stress to the tensile pressure and is determined from the slope of a stress-tension curve. For example, the film typically exhibits an MD and / or CD elastic modulus of about 2,500 Megapascals ("MPa") or less, in some embodiments about 2200 MPa or less, in some embodiments of about 50 MPa to about 2,000 MPa, and in some embodiments, from about 100 MPa to about 1,000 MPa. The modulus of elasticity can be determined in accordance with the ASTM D638-10 standard, at 23 ° C.
[0064] Although the film is ductile, it can still be relatively resistant. A parameter that is indicative of the relative intensity of the film is the stress resistance, which is equal to the peak stress obtained in a stress-strain curve, as obtained according to the ASTM D638-10 standard. For example, the film of the present invention may have a peak stress MD and / or CD of about 5 MPa to about 65 MPa, in some embodiments of about 10 MPa to about 60 MPa, and in some forms from about 20 MPa to about 55 MPa. The film may also exhibit a tensile strength MD and / or CD of about 5 MPa to about 60 MPa, in some embodiments from about 10 MPa to about 50 MPa, and in some embodiments, from from about 20 MPa to about 45 MPa. The peak voltage and breaking voltage can be determined according to the ASTM D638-10 standard at 23 ° C.
[0065] If desired, the film of the present invention can be subjected to one or more additional processing steps. Examples of such processes include, for example, notch roller drawing, perforation, embossing, coating, etc. The film can also be the surface treated using any of a variety of techniques known to improve its properties. For example, high-energy beams (eg plasma, x-rays, electron beams, etc.) can be used to remove or reduce any surface layer that forms the film, to change the surface's polarity, porosity, topography, etc.
[0066] The film can also be laminated with one or more coatings of non-woven fabric to reduce the coefficient of friction and increase the sensation of common fabric on the surface of the compound. Examples of polymers for use in forming non-woven fabric coatings may include, for example, polyolefins such as polyethylene, polypropylene, polybutylene, etc .; 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; polylactic acid; copolymers of these; and so on. If desired, renewable polymers, such as those described above, can also be employed. Synthetic or natural cellulosic polymers can also be used, including, but not limited to, cellulose esters; cellulose ethers; cellulose nitrates; cellulose acetates; cellulosic acetate butyrates; ethyl cellulose; regenerated celluloses, such as viscose, rayon, and so on. It should be noted that the polymers can also contain other additives, such as processing aids or treatment compositions to impart the desired properties to the fibers, residual amounts of solvents, pigments or dyes, and so on.
[0067] Monocomponent and / or multicomponent fibers can be used to form the lining of non-woven fabric. Mono-component fibers are generally formed from a polymer or mixture of polymers extruded from a single extruder. Multicomponent fibers are generally formed from two or more polymers (for example, bicomponent fibers) from extrudates from separate extruders. The polymers can be disposed in substantially distinct areas and constantly positioned across the cross section of the fibers. The components can be arranged in any desired configuration, such as a sheath core, winged side, pizza, island in the sea, three islands, porthole or other arrangements known in the art. Multicomponent fibers having various irregular shapes can also be formed.
[0068] Fibers of any desired length can be used, such as basic fibers, continuous fibers, etc. In a particular embodiment, for example, basic fibers can be used having a fiber length in the range of about 1 to about 150 millimeters, in some embodiments from about 5 to about 50 millimeters, in some forms from about 10 to about 40 millimeters, and in some embodiments, from about 10 to about 25 millimeters. Although not necessary, carding techniques can be employed to form fibrous layers with basic fibers, as is well known in the art. For example, fibers can form a carded fabric by placing bales of fibers in a picker that separates the fibers. Then, the fibers are sent through a combing or carding unit that breaks and aligns the fibers towards the machine, in order to form a fibrous non-woven fabric oriented towards the machine. The carded fabric can then be glued, using known techniques, to form a glued carded non-woven fabric.
[0069] If desired, the non-woven fabric lining used to form the non-woven composite can have a multilayer structure. Suitable multilayer materials can include, for example, spunbond / meltblown / spunbond (SMS) laminates and laminates and spunbond / meltblown. Another example of a multilayer structure is a spunbond fabric produced in a multi-rotating bench machine in which a rotating bench deposits fibers on a layer of fibers deposited from an anterior rotating bench. Such individual non-woven spunbond fabric can also be thought of as a multilayered structure. In this situation, the various layers of fibers deposited in non-woven fabric can be the same or they can be different in basis weight and / or in terms of the composition, type, size, degree of waviness and / or the shape of the fibers produced. As another example, a single non-woven fabric can be provided in two or more layers produced individually from a spunbond fabric, a carded fabric, etc., which have been joined together to form a non-woven fabric. These layers produced may differ, individually, in terms of production method, base weight, composition and fibers, as discussed above. A nonwoven covering fabric may also contain an additional fibrous component which is considered to be a compound. For example, a nonwoven fabric can be wrapped with another fibrous component using any of a variety of entanglement techniques known in the art (for example, hydraulics, pneumatics, mechanics, etc.). In one embodiment, the non-woven fabric is integrally wrapped with cellulosic fibers that use hydraulic entanglement. A typical hydraulic entanglement process uses high pressure water jets to entangle the fibers to form a highly entangled fibrous structure, for example, a nonwoven fabric. The fibrous component of the compound can contain any desired amount of the resulting substrate.
[0070] The base weight of the non-woven fabric lining can generally vary, for example, from about 5 grams per square meter ("gsm") to 120 gsm, in some embodiments from about 8 to 70 gsm, and in some embodiments, from about 10 gsm to 35 gsm. When using multiple coatings of non-woven fabric, these materials may have the same or different base weights. IV. applications
[0071] The film of the present invention can be used in a wide variety of applications, such as a packaging film, as an individual wrapper, packaging pouch or bag for the disposal of a variety of articles, such as food products, paper products ( eg fabrics, tissues, paper towels, etc.), absorbent articles, etc. Various configurations of pouch, wrap or bag suitable for absorbent articles are disclosed, for example, in U.S. Patent No. 6,716,203 to Sorebo et al. and 6,380,445 to Moder et al., as well as U.S. Patent Application No. 2003/0116462 to Sorebo et al.
[0072] The film can also be used in other applications. For example, the film can be used on an absorbent article. An "absorbent article" generally refers to any article capable of absorbing water or other fluids. Examples of some absorbent articles include, but are not limited to, absorbent personal care articles, such as diapers, training pants, absorbent incontinence briefs, articles, feminine hygiene products (for example, intimate pads), swimwear, wipes moistened, and so on; medical absorbent articles, such as clothing, fenestration materials, bed pads, bandages, absorbent curtains, medical wipes; food service cleaners; clothing items; and so on. Several examples of absorbent articles are described in U.S. Patent No. 5,649,916 to DiPalma et al .; 6,110,158 for Kielpikowski; 6,663,611 to Blaney et al. Still other suitable articles are described in U.S. Patent Application Publication No. 2004/0060112 A1 to Fell et al., As well as in U.S. Patent No. 4,886,512 to Damico et al .; 5,558,659 to Sherrod et al. ; 6,888,044 to Fell et al. ; and 6,511,465 for Freiburger et al. Suitable materials and processes for forming such absorbent articles are well known to those skilled in the art.
[0073] In this regard, a specific embodiment of an absorbent article that can employ the film of the present invention will now be described in more detail. For example, the absorbent article may include a main body portion that contains an upper layer, an outer cover or back layer, an absorbent core positioned between the lower layer and the upper layer, and a pair of flaps extending from each longitudinal side of the main body. The upper layer defines a surface that touches the body of the absorbent article. The absorbent core is positioned inwardly from the outer edge of the absorbent article and includes a body-facing side adjacent to the top layer and a clothing-facing surface positioned adjacent to the bottom layer. In a particular embodiment of the present invention, the backsheet is a film formed from the thermoplastic composition of the present invention and is generally impermeable to liquids and vapor permeable, optionally. The film used to form the backsheet can also be laminated with one or more non-woven fabric coatings as described above.
[0074] The upper layer is generally designed to contact the user's body and is permeable to liquids. The top layer can wrap around the absorbent core so that it completely coats the absorbent article. Alternatively, the top layer and the bottom layer can extend beyond the absorbent core and be joined peripherally together, in whole or in part, using known techniques. Generally, the top layer and the back layer are joined by adhesive bonding, ultrasonic bonding or any other joining method known in the art. The top layer is hygienic and clean in appearance and slightly opaque to hide the body discharges collected and absorbed by the absorbent core. The top layer also has good removal and re-humidification characteristics, allowing body discharges to quickly penetrate through the top layer to the absorbent core, but does not allow body fluid to pass back through the top layer to the user's skin. . For example, some suitable materials that can be used for the top layer include non-woven materials, perforated thermoplastic films or combinations thereof. A non-woven fabric made of polyester, polyethylene, polypropylene, bicomponent, nylon, rayon or similar fibers can be used. For example, a white spunbond material is particularly desirable, because the color exhibits good masking properties to hide menstruation that has passed through it. US patents no. 4,801,494 to Datta, et al. and 4,908,026 to Sukiennik, et al. teach the various other coating materials that can be used in the present invention.
[0075] The top layer may also include a plurality of openings formed through it to allow fluid in the body to pass more easily into the absorbent core. The openings can be arranged randomly or uniformly along the top layer, or they can be located only in the narrow longitudinal strip or arranged in line along the longitudinal axis of the absorbent article. The openings allow the rapid penetration of body fluid into the absorbent core. The size, shape, diameter and number of openings can vary to meet the specific needs of each person.
[0076] The absorbent article may also contain an absorbent core positioned between the top layer and the back layer. The absorbent core can be formed from a single absorbent element or a compound that contains separate and distinct absorbent elements. It should be understood, however, that any number of absorbent elements can be used in the present invention. For example, in one embodiment, the absorbent core may contain a receiving element positioned between the top layer and a transfer delay element. The receiving element can be made of a material that is able to quickly transfer, in the z direction, the body fluid that is delivered to the upper layer. The receiving element can generally be of any desired shape and / or size. In one embodiment, the receiving element has a rectangular shape, with a length equal to or less than the total length of the absorbent article, and a width less than the width of the absorbent article. For example, a length between 150 mm and about 300 mm, and a width between 10 mm and about 60 mm can be used.
[0077] Any of a variety of different materials can be used for the receiving element to perform the functions mentioned above. The material can be synthetic, cellulose or a combination of both. For example, airlaid cellulosic fabrics may be suitable for the receiving component. Airlaid cellulosic fabric can have a base weight ranging from about 10 grams per square meter (g / m2) to about 300 g / m2, and in some embodiments, between about 100 g / m2 to about 250 g / m2. In one embodiment, the cellulosic airlaid fabric has a base weight of about 200 g / m 2. Airflow fabric can be made of hardwood and / or softwood fibers. The air-formed tissue has a fine pore structure and provides excellent evaporation capacity, especially for menstruation.
[0078] If desired, a transfer delay element can be positioned vertically below the receiving element. The transfer delay element can contain a material that is less hydrophilic than the other absorbent elements, and can generally be characterized as being substantially hydrophobic. For example, the transfer delay element may be a fibrous nonwoven fabric consisting of a relatively hydrophobic material, such as polypropylene, polyethylene, polyester or the like, and may also be composed of a mixture of these materials. An example of a material suitable for the transfer delay element is a woven material in a rolled form composed of polypropylene fibers with several lobes. Other examples of suitable transfer delay element materials include spunbond fabrics composed of polypropylene fibers, which can be round, tri-local or poly-lobal-shaped in cross-section and which can be hollow or solid in their structure. Normally, the wefts are joined, for example, by thermal bonding, above 3% to about 30% of the web area. Other examples of suitable materials that can be used for the transfer delay element are described in U.S. Patent No. 4,798,603 to Meyer et al. and 5,248,309 for Serbiak et al. To adjust the performance of the invention, the transfer delay element can also be treated with a selected amount of surfactant to increase its initial wettability.
[0079] The transfer delay element can generally be of any size, such as a length of about 150 mm to 300 mm. Typically, the length of the transfer delay element is approximately equal to the length of the absorbent article. The transfer delay element can also be equal to the width of the receiving element, but is typically wider. For example, the width of the transfer delay element can be between about 50 mm to 75 mm and, in particular, about 48 mm. The transfer delay element typically has a lower base weight than that of the other absorbent elements. For example, the base weight of the transfer delay element is typically less than about 150 grams per square meter (g / m2) and, in some embodiments, between about 10 g / m2 to 100 g / m2. In a particular embodiment, the transfer delay element is formed from a spundbond fabric with a basis weight of about 30 g / m2.
[0080] In addition to the elements mentioned above, the absorbent core may also include a composite absorbent element, such as a co-formed material. In this case, fluids can be absorbed from the transfer delay element to the composite absorbent element. The composite absorbent element can be formed separately from the receiving element and / or transfer delay element or can be formed simultaneously with it. In one embodiment, for example, the composite absorbent element can be formed on the transfer delay element or receiving element, which acts as a vehicle, during the co-forming process described above.
[0081] Although various configurations of an absorbent article have been described above, it should be understood that other configurations are also included within the scope of the present invention. Furthermore, the present invention is by no means limited to the back layers and the film of the present invention can be incorporated into a variety of different components of an absorbent article. For example, an absorbent article release liner may include the film of the present invention.
[0082] The present invention can be better understood with reference to the following examples. Test methods Fusion flow rate:
[0083] The melt flow rate ("MFR") is the weight of a polymer (in grams) forced through an extrusion rheometer orifice (0.0825 inch diameter) when subjected to a load of 2,160 grams in 10 minutes, typically 190 ° C or 230 ° C, unless otherwise stated, the melt flow rate is measured according to the ASTM D1239 test method with a Tinius Olsen extrusion plastomer. Thermal properties:
[0084] The glass transition temperature (Tg) can be determined by means of dynamic-mechanical analysis (DMA), according to the ASTM E1640-09 standard. A TA Instruments Q800 instrument can be used. Experimental tests can be performed on voltage / voltage geometry, in a temperature sweep mode in the range of -120 ° C to 150 ° C with a heating rate of 3 ° C / min. The voltage amplitude frequency can be kept constant (2 Hz) during the test. Three (3) independent samples can be tested to obtain an average glass transition temperature, which is defined by the peak value of the tangent curve δ, where the tangent δ is defined as the ratio of the loss module to the storage module. (tangent δ = E ”/ E ').
[0085] The melting temperature can be determined by differential scanning calorimetry (DSC). The differential scanning calorimeter can be a DSC Q100 calorimeter, which has been equipped with a liquid nitrogen cooling accessory and UNIVERSAL ANALYSIS 2000 analysis software (version 4.6.6), which are available from TA Instruments Inc. of New Castle , Delaware. To avoid handling samples directly, tweezers or other instruments 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 folded over the sample material over the pan. Typically, the resin pellets are placed directly in the weighing container.
[0086] The differential scanning calorimeter is calibrated using an Indian metal standard and a baseline correction is performed, as described in the instruction manual for the differential scanning calorimeter. A sample of material is placed in the test chamber of the differential scanning calorimeter for testing, and an empty container is used as a reference. All tests are performed with a 55 cubic cm per minute nitrogen (industrial grade) purge in the test chamber. For resin pelletizing samples, the heating and cooling program is a 2-cycle test that begins with a chamber equilibrium at -30 ° C, followed by a first heating period at a heating rate of 10 ° C per minute to 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 to a temperature of -30 ° C, followed by equilibrating the sample at -30 ° C for 3 minutes, and then a second heating period at a heating rate of 10 ° C per minute to a temperature of 200 ° C. All tests are performed with a purge of 55 cubic centimeters per minute nitrogen (industrial grade) in the test chamber.
[0087] The results are evaluated using the UNIVERSAL ANALYSIS 2000 analysis software, which identifies and quantifies the inflection glass transition temperature (Tg), the endothermic and exothermic peaks, and the areas under the peaks in the DSC graphs. The glass transition temperature is identified as the region in the narrative line where a clear change in slope has occurred, and the melting temperature is determined through an automatic inflection calculation. Traction properties
[0088] The films were tested for tensile properties (peak stress, modulus, rupture stress, and energy per rupture volume) on an MTS Synergie 200 traction frame. The test was carried out in accordance with ASTM D638 -10 (at about 23 ° C). The film samples were cut into dog bone shapes with a center width of 3.0 millimeters before the test. Dog bone film samples were taken on site using the handles on the MTS Synergie 200 device with a useful length of 18.0 mm. The film samples were stretched at a crosshead speed of 5.0 in./min., Until rupture occurred. Five samples were tested for each film in both the machine (DM) and transverse (CD) directions. A computer program called TestWorks 4 was used to collect data during the tests and to generate stress compared to the stress curve from which a number of properties were determined, including the modulus of elasticity, peak stress, elongation and energy until the break. Moisture content
[0089] 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 herein in its entirety by reference to all purposes. The test temperature (§X2.1.2) can be 130 ° C, the sample size (§X2.1.1) can be 2 g to 4 grams, and the vial purging time (§X2.1.4) can be 30 seconds. In addition, the final criteria (§X2.1.3) can be defined as a "prediction" mode, which means that the test ends when the internally programmed criteria (which mathematically calculate the final moisture point) are met. EXAMPLE 1
[0090] Films formed from 100% polylactic acid (PLA) were formed as a control by extruding PLA 6201D (Natureworks®, 10 g / 10 minutes melt index at 190 ° C) onto a film . The pellets were inserted into a Rheomix 252 signal screw extruder with a C: D ratio of 25: 1, which was heated to a temperature of about 208 ° C, where the molten mixture came out through a molten film mold. 6 inches wide and stretched with a take-up reel to form a film with a thickness of 41.9 μm to 48.3 μm. EXAMPLE 2
[0091] The ability to form films from a mixture of 88.7% polylactic acid (PLA 6201D, Natureworks®) 9.9% of a curing additive and 1.4% of polyepoxide modifier has been demonstrated. The curing additive was Vistamaxx ™ 2120 (ExxonMobil), which is a copolymer / polyolefin elastomer with a melt flow rate of 29 g / 10 min (190 ° C, 2,160 g) and a density of 0.866 g / cm3. The polyepoxide modifier was a poly (ethylene-co-methyl acrylate-co-glycidyl methacrylate) (Lotader ® AX8950, Arkema) having a melt flow rate of 70 to 100 g / 10 min (190 ° C / 2160 g) , glycidyl methacrylate content gives 7% to 11% by weight, methyl acrylate content from 13% to 17% by weight, and ethylene content from 72% to 80% by weight. The polymers were fed into a co-rotating twin screw extruder (ZSK-30, diameter 30 mm, length 1328 mm), the composition of which was manufactured by Werner and Pfleiderer Corporation, of Ramsey, New Jersey. The extruder had 14 zones, numbered from 1 to 14 from the feed tank to the die. The first zone of barrel # 1 received the resins through the gravimetric feeder at a total transfer rate of 15 pounds per hour. The mold used for the extrusion of the resin had 3 openings (6 millimeters in diameter), which were separated by 4 millimeters. After forming, the extruded resin was cooled on a conveyor belt with ventilation and molded into pellets by a Conair pelletizer. The screw speed of the extruder was 200 revolutions per minute (“rpm”). The pellets were then inserted into a Rheomix 252 signal screw extruder with a C: D ratio of 25: 1, which was heated to a temperature of about 212 ° C, where the molten mixture came out through a film mold 6 inch wide Haake cast and stretched to form a 39.4 μm to 50.8 μm thick film using a Haake take-up roller. EXAMPLE 3
[0092] The films were formed as described in Example 2, except that the mixture contained 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of additive Vistamaxx ™ 2120 (ExxonMobil) hardening, 1.4% by weight of polyepoxide modifier (Lotader® AX8950, Arkema) and 3.8% by weight of the internal interfacial modifier (BASF Pluriol® WI 285 basic stock lubricant). PLURIOL® WI285 was added via an injection pump in barrel zone no. 2. The films were stretched to a thickness ranging from 38.1 μm to 45.7 μm. SEM photomicrographs were taken from Example 3, before and after the test. The results are shown in Figs. 2 and 3. As shown, the PLA matrix of Example 3 underwent displacement, which resulted in the formation of a plurality of voids adjacent to the separate domains of the Vistamaxx ™ polymer. EXAMPLE 4
[0093] The films were formed as described in Example 3, except that they were designed for a thickness of 110.5 μm to 171.5 μm.
[0094] Various mechanical properties were tested for the films of Examples 1 to 4, as described above. The results are shown below in Table 1. Table 1: Film properties of Examples 1 to 4

权利要求:
Claims (15)
[0001]
1. Film comprising a thermoplastic composition, characterized by the fact that the thermoplastic composition comprises: 70% or more by weight, based on the total weight of the thermoplastic composition, of at least one renewable rigid polyester having a glass transition temperature of 0 ° C or superior; from 1% by weight to 30% by weight of at least one polymeric curing additive, based on the weight of the renewable polyester, wherein the polymeric curing additive includes a polyolefin; from 0.1% by weight to 20% by weight of at least one interphasic modifier, based on the weight of the renewable polyester, where the interphasic modifier is a silicone, silicone-polyether copolymer, aliphatic polyester, aromatic polyester, alkylene glycol , alkane diol, amine oxide, fatty acid ester or a combination thereof; and at least one polyepoxide modifier having an average numerical molecular weight of 7,500 to 250,000 g / mol; wherein the thermoplastic composition has a morphology in which a plurality of discrete primary domains are dispersed within a continuous phase, the domains containing the polymeric curing additive and the continuous phase containing the renewable polyester; where the film has a tension module in the machine direction and in the transversal direction of the machine of 2,500 Megapascals or less, an elongation by tension in the machine direction of 10% or more, and an elongation by tension in the direction of rupture cross-section of the machine of 15% or more, where the stress modulus and stress elongation at break are determined at 23 ° C, according to ASTM D638-10, where the ratio of the glass transition temperature of the composition thermoplastic and the glass transition temperature of the renewable polyester is 0.7 to 1.3.
[0002]
2. Film according to claim 1, characterized by the fact that the renewable polyester is a polylactic acid or a polyethylene terephthalate.
[0003]
Film according to claim 1 or 2, characterized in that the renewable polyester and the thermoplastic composition have a glass transition temperature of 50 ° C to 75 ° C.
[0004]
4. Film according to any one of the preceding claims, characterized by the fact that the ratio between the renewable polyester solubility parameter and the polymeric curing additive solubility parameter is 0.5 to 1.5, the ratio between the melt flow rate of the renewable polyester and the melt flow rate of the polymeric curing additive is 0.2 to 8, and the ratio between the Young elastic modulus of the renewable polyester and the Young elastic modulus of the polymeric curing additive is 2 to 500.
[0005]
Film according to any one of the preceding claims, characterized in that the polyolefin is a propylene homopolymer, an alpha-olefin / propylene copolymer, an ethylene / alpha-olefin copolymer, or a combination thereof.
[0006]
6. Film according to any one of the preceding claims, characterized by the fact that the interphasic modifier has a kinematic viscosity of 0.7 to 200 centistokes, determined at a temperature of 40 ° C.
[0007]
7. Film according to any one of the preceding claims, characterized by the fact that the interphasic modifier is hydrophobic.
[0008]
8. Film according to any one of the preceding claims, characterized by the fact that the discrete domains have a length of 0.05 micrometers to 30 micrometers.
[0009]
9. Film according to any one of the preceding claims, characterized by the fact that the polyepoxide modifier includes an epoxy-functional monomeric (meta) acrylic component.
[0010]
10. Film according to claim 9, characterized by the fact that the polyepoxide modifier includes poly (ethylene-CO-methacrylate-CO-glycidyl methacrylate).
[0011]
11. Film according to any one of the preceding claims, characterized by the fact that the renewable polyester constitutes 75% by weight to 98% by weight of the thermoplastic composition.
[0012]
12. Film according to any one of the preceding claims, characterized by the fact that the film has a tension module in the machine direction and in the transversal direction of the machine from 50 to 2,000 Megapascals, determined at 23 ° C, according to ASTM D638-10; and / or in which the film has a stress elongation at break in the machine direction from 100% to 600% and a stress elongation at break in the transversal direction of the machine from 100% to 400%, determined at 23 ° C, according to with ASTM D638-10.
[0013]
13. Film according to any one of the preceding claims, characterized by the fact that the film has a thickness of 1 to 200 micrometers.
[0014]
14. Film according to any one of the preceding claims, characterized in that the film is a multilayer film and contains a basic layer and at least one additional layer, wherein the basic layer contains the thermoplastic composition.
[0015]
15. Absorbent article, characterized in that it comprises a layer generally impermeable to liquids, the layer comprising the film as defined in any one of claims 1 to 14; the article comprising an absorbent core positioned between the generally liquid-impermeable layer and a liquid-permeable layer, wherein the film is bonded to a non-woven web material.

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公开号 | 公开日

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RU2618561C2|2017-05-04|

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AU2013217366A1|2014-07-24|

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EP2812381B1|2018-05-09|

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RU2014134788A|2016-03-27|

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KR20200032754A|2020-03-26|

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AU2013217366B2|2016-04-07|

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US20130209770A1|2013-08-15|

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EP2812381A4|2015-10-07|

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KR20140127817A|2014-11-04|

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JP6153208B2|2017-06-28|

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CN104144974A|2014-11-12|

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WO2013118023A1|2013-08-15|

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CN104144974B|2017-11-28|

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EP2812381A1|2014-12-17|

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JP2015510537A|2015-04-09|

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US20150159012A1|2015-06-11|

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KR102209321B1|2021-01-29|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3338992A|1959-12-15|1967-08-29|Du Pont|Process for forming non-woven filamentary structures from fiber-forming synthetic organic polymers|

---

US3341394A|1966-12-21|1967-09-12|Du Pont|Sheets of randomly distributed continuous filaments|

---

DE1939528A1|1969-08-02|1971-02-11|Barmag Barmer Maschf|Device for the continuous production of multilayer blown films|

---

DE1950669C3|1969-10-08|1982-05-13|Metallgesellschaft Ag, 6000 Frankfurt|Process for the manufacture of nonwovens|

---

US3726955A|1971-01-11|1973-04-10|Phillips Petroleum Co|Process for producing filaments and yarns of blended incompatible polymers|

---

CA982320A|1971-05-20|1976-01-27|David Gibson|Voided polyester fiber|

---

US4055702A|1974-03-29|1977-10-25|M & T Chemicals Inc.|Additive-containing fibers|

---

US4937299A|1983-06-06|1990-06-26|Exxon Research & Engineering Company|Process and catalyst for producing reactor blend polyolefins|

---

US4707398A|1986-10-15|1987-11-17|Kimberly-Clark Corporation|Elastic polyetherester nonwoven web|

---

ES2052551T3|1986-12-19|1994-07-16|Akzo Nv|METHOD FOR PREPARING POLY OR POLY COPOLYMERS BY POLYMERATION OF THE LACTIDE.|

---

US5069970A|1989-01-23|1991-12-03|Allied-Signal Inc.|Fibers and filters containing said fibers|

---

US5162074A|1987-10-02|1992-11-10|Basf Corporation|Method of making plural component fibers|

---

US5502158A|1988-08-08|1996-03-26|Ecopol, Llc|Degradable polymer composition|

---

US5218071A|1988-12-26|1993-06-08|Mitsui Petrochemical Industries, Ltd.|Ethylene random copolymers|

---

JP2682130B2|1989-04-25|1997-11-26|三井石油化学工業株式会社|Flexible long-fiber non-woven fabric|

---

US5057368A|1989-12-21|1991-10-15|Allied-Signal|Filaments having trilobal or quadrilobal cross-sections|

---

KR960004143B1|1990-04-10|1996-03-27|도오요오 보오세끼 가부시끼가이샤|A void-containing polyester film, and its laminate|

---

US5317059A|1990-07-09|1994-05-31|Ferro Corporation|Impact-resistant polymer blends of olefin polymers, polyamides, and terpolymer compatibilizers|

---

US5266610A|1991-03-11|1993-11-30|Ici Composites Inc.|Toughened cocontinuous resin system|

---

DE4119857A1|1991-06-17|1992-12-24|Basf Lacke & Farben|COATING AGENTS BASED ON CARBOXYL GROUP-CONTAINING POLYMERS AND EPOXY RESINS|

---

US5277976A|1991-10-07|1994-01-11|Minnesota Mining And Manufacturing Company|Oriented profile fibers|

---

US5278272A|1991-10-15|1994-01-11|The Dow Chemical Company|Elastic substantialy linear olefin polymers|

---

US5272236A|1991-10-15|1993-12-21|The Dow Chemical Company|Elastic substantially linear olefin polymers|

---

US6326458B1|1992-01-24|2001-12-04|Cargill, Inc.|Continuous process for the manufacture of lactide and lactide polymers|

---

US5470944A|1992-02-13|1995-11-28|Arch Development Corporation|Production of high molecular weight polylactic acid|

---

US5939467A|1992-06-26|1999-08-17|The Procter & Gamble Company|Biodegradable polymeric compositions and products thereof|

---

US5382400A|1992-08-21|1995-01-17|Kimberly-Clark Corporation|Nonwoven multicomponent polymeric fabric and method for making same|

---

US5336552A|1992-08-26|1994-08-09|Kimberly-Clark Corporation|Nonwoven fabric made with multicomponent polymeric strands including a blend of polyolefin and ethylene alkyl acrylate copolymer|

---

US5322728A|1992-11-24|1994-06-21|Exxon Chemical Patents, Inc.|Fibers of polyolefin polymers|

---

IT1256260B|1992-12-30|1995-11-29|Montecatini Tecnologie Srl|ATACTIC POLYPROPYLENE|

---

US5359026A|1993-07-30|1994-10-25|Cargill, Incorporated|Poly copolymer and process for manufacture thereof|

---

US5472775A|1993-08-17|1995-12-05|The Dow Chemical Company|Elastic materials and articles therefrom|

---

US5571619A|1994-05-24|1996-11-05|Exxon Chemical Patents, Inc.|Fibers and oriented films of polypropylene higher α-olefin copolymers|

---

AT176786T|1994-11-08|1999-03-15|Basf Corp|METHOD FOR SEPARATING POLYMERS FROM POLYMER BLENDS|

---

US5714573A|1995-01-19|1998-02-03|Cargill, Incorporated|Impact modified melt-stable lactide polymer compositions and processes for manufacture thereof|

---

US5539056A|1995-01-31|1996-07-23|Exxon Chemical Patents Inc.|Thermoplastic elastomers|

---

DE69631305T2|1995-07-25|2004-11-18|Toyota Jidosha K.K., Toyota|Process for the production of polylactic acid|

---

US5770682A|1995-07-25|1998-06-23|Shimadzu Corporation|Method for producing polylactic acid|

---

US5726220A|1995-08-30|1998-03-10|Shin-Etsu Chemical Co., Ltd.|Biodegradable polymer compositions and shrink films|

---

JPH09151310A|1995-08-30|1997-06-10|Shin Etsu Chem Co Ltd|Polymer composition having biodegradability and shrink film|

---

FI105040B|1996-03-05|2000-05-31|Neste Oy|The polylactide film|

---

JP3588907B2|1996-03-22|2004-11-17|トヨタ自動車株式会社|Method for producing polylactic acid|

---

US5844067A|1996-04-18|1998-12-01|Erneta; Modesto|Process for producing absorbable segmented copolymers with a substantially uniform sequence distribution|

---

JPH09291203A|1996-04-26|1997-11-11|Kuraray Co Ltd|Polyester resin composition|

---

US5948528A|1996-10-30|1999-09-07|Basf Corporation|Process for modifying synthetic bicomponent fiber cross-sections and bicomponent fibers thereby produced|

---

US6200669B1|1996-11-26|2001-03-13|Kimberly-Clark Worldwide, Inc.|Entangled nonwoven fabrics and methods for forming the same|

---

US6309988B1|1997-12-22|2001-10-30|Kimberly-Clark Worldwide, Inc.|Biodisintegratable nonwovens with improved fluid management properties|

---

US5883199A|1997-04-03|1999-03-16|University Of Massachusetts|Polyactic acid-based blends|

---

US6183814B1|1997-05-23|2001-02-06|Cargill, Incorporated|Coating grade polylactide and coated paper, preparation and uses thereof, and articles prepared therefrom|

---

GB9719060D0|1997-09-09|1997-11-12|Ici Plc|Polymer composition|

---

EP1252376A1|1999-11-09|2002-10-30|Kimberly-Clark Worldwide, Inc.|Biodegradable polylactide nonwovens with fluid management properties and disposable absorbent products containing the same|

---

MXPA02001354A|1999-08-25|2002-07-22|Kimberly Clark Co|Biodisintegratable nonwovens with fluid management properties and disposable absorbent products containing same.|

---

EP0980894B1|1998-03-05|2004-06-23|Mitsui Chemicals, Inc.|Polylactic acid composition and film thereof|

---

US6509092B1|1999-04-05|2003-01-21|Fiber Innovation Technology|Heat bondable biodegradable fibers with enhanced adhesion|

---

US6500563B1|1999-05-13|2002-12-31|Exxonmobil Chemical Patents Inc.|Elastic films including crystalline polymer and crystallizable polymers of propylene|

---

DE60018635T2|1999-05-21|2006-04-13|Toyota Jidosha K.K., Toyota|Monofilament and process for its preparation|

---

JP3258302B2|1999-10-26|2002-02-18|三菱樹脂株式会社|Biodegradable biaxially stretched film|

---

EP1302509B1|2000-07-17|2009-03-11|Mitsui Chemicals, Inc.|Lactic acid-base resin compositions and molded articles made thereof|

---

US6914018B1|2000-10-27|2005-07-05|Kimberly-Clark Worldwide, Inc.|Biaxial stretch, breathable laminate with cloth-like aesthetics and method for making same|

---

US6838403B2|2000-12-28|2005-01-04|Kimberly-Clark Worldwide, Inc.|Breathable, biodegradable/compostable laminates|

---

US20030162013A1|2001-04-23|2003-08-28|Topolkaraev Vasily A.|Articles comprising biodegradable films having enhanced ductility and breathability|

---

US6905759B2|2001-04-23|2005-06-14|Kimberly Clark Worldwide, Inc.|Biodegradable films having enhanced ductility and breathability|

---

US6660211B2|2001-04-23|2003-12-09|Kimberly-Clark Worldwide, Inc.|Methods of making biodegradable films having enhanced ductility and breathability|

---

CN100347355C|2001-06-15|2007-11-07|可乐丽股份有限公司|Composite fiber|

---

US20030039775A1|2001-08-17|2003-02-27|Dan-Cheng Kong|Multilayer sleeve labels|

---

US20030153684A1|2001-11-28|2003-08-14|Hitech Polymers Inc.|Polyester composition|

---

US20030105231A1|2001-11-28|2003-06-05|Hitech Polymers Inc.|Polyester composition|

---

US20030106568A1|2001-12-12|2003-06-12|Kimberly-Clark Worldwide, Inc.|Cleaning sheet, system and apparatus|

---

US6984694B2|2002-02-01|2006-01-10|Johnson Polymer, Llc|Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications|

---

US7256223B2|2002-11-26|2007-08-14|Michigan State University, Board Of Trustees|Environmentally friendly polylactide-based composite formulations|

---

US6869985B2|2002-05-10|2005-03-22|Awi Licensing Company|Environmentally friendly polylactide-based composite formulations|

---

US7994078B2|2002-12-23|2011-08-09|Kimberly-Clark Worldwide, Inc.|High strength nonwoven web from a biodegradable aliphatic polyester|

---

US7135523B2|2003-03-14|2006-11-14|Industrial Technology Research Institute|Nanoscale helical microstructures and channels from chiral poly block containing block copolymers|

---

US7514503B2|2003-10-08|2009-04-07|Asahi Kasei Chemicals Corporation|Molded article produced from aliphatic polyester resin composition|

---

US7157032B2|2003-11-21|2007-01-02|Gala Industries, Inc.|Method and apparatus for making crystalline PET pellets|

---

US20050112363A1|2003-11-21|2005-05-26|Xin Ning|Biodegradable polymer compositions for a breathable film|

---

US7273894B2|2003-12-02|2007-09-25|Eastman Chemical Company|Compositions for the preparation of void-containing articles|

---

US6949288B2|2003-12-04|2005-09-27|Fiber Innovation Technology, Inc.|Multicomponent fiber with polyarylene sulfide component|

---

US7354973B2|2003-12-12|2008-04-08|E.I. Du Pont De Nemours And Company|Toughened poly compositions|

---

US7595363B2|2003-12-12|2009-09-29|E.I. Du Pont De Nemours And Company|Toughened poly compositions|

---

US7368503B2|2003-12-22|2008-05-06|Eastman Chemical Company|Compatibilized blends of biodegradable polymers with improved rheology|

---

US7393590B2|2004-02-27|2008-07-01|Cereplast, Inc.|Biodegradable poly polymer composition and films, coatings and products comprising Biodegradable poly polymer compositions|

---

US7138439B2|2004-02-27|2006-11-21|Biocorp North America, Inc.|Biodegradable compounds including poly polymer compositions and products|

---

BRPI0512370B1|2004-06-23|2018-01-30|Natureworks Llc|PROCESS FOR INTRODUCING LONG CHAIN RAMIFICATION IN A FUSION PROCESSABLE POLYLATIDE RESIN|

---

JP5004068B2|2004-11-26|2012-08-22|独立行政法人産業技術総合研究所|Polylactic acid resin composition and method for producing polylactic acid resin composition|

---

US7619132B2|2004-12-30|2009-11-17|Kimberly-Clark Worldwide, Inc.|Degradable breathable multilayer film with improved properties and method of making same|

---

US20090068463A1|2005-10-19|2009-03-12|Katsuhiko Mochizuki|Crimped Yarn, Method for Manufacture thereof, and Fiber Structure|

---

CN101360789B|2005-11-25|2011-09-07|可乐丽股份有限公司|Polylactic acid composition|

---

JP5033326B2|2005-12-12|2012-09-26|三菱樹脂株式会社|Heat-shrinkable pore-containing film, molded article using the film, heat-shrinkable label, and container|

---

EP1966419B1|2005-12-15|2010-09-15|Kimberly-Clark Worldwide, Inc.|Biodegradable multicomponent fibers|

---

EP1967542A4|2005-12-26|2010-09-22|Nisshin Spinning|Polyolefin/polyester film|

---

WO2007092417A1|2006-02-07|2007-08-16|Tepha, Inc.|Toughened polylactic acid polymers and copolymers|

---

CN101384662A|2006-02-14|2009-03-11|日本电气株式会社|Polylactic acid resin composition and molded item|

---

KR101366603B1|2006-03-03|2014-03-14|아크조 노벨 엔.브이.|Process for the modification of biodegradable polymers|

---

JP2007269995A|2006-03-31|2007-10-18|Three M Innovative Properties Co|Polylactic acid-containing resin composition, polylactic acid-containing resin film, and polylactic acid-containing resin fiber|

---

JP2007270076A|2006-03-31|2007-10-18|Tohcello Co Ltd|Polylactic acid type stretched film, stretched laminated film and its use|

---

US8927443B2|2006-04-07|2015-01-06|Kimberly-Clark Worldwide, Inc.|Biodegradable nonwoven laminate|

---

FR2902433A1|2006-06-16|2007-12-21|Arkema France|Composite, useful to make e.g. molded-, extruded- and thermoformed object to make parts of mobile telephone and computer, comprises polymer composition of polylactic acid matrix, polyamide, functionalized polyolefin, and polyoxymethylene|

---

FR2902434B1|2006-06-16|2008-08-01|Arkema France|POLYLACTIC ACID COMPOSITION HAVING ENHANCED SHOCK RESISTANCE|

---

TWI323739B|2006-06-27|2010-04-21|Far Eastern New Century Corp|

---

US9089627B2|2006-07-11|2015-07-28|Abbott Cardiovascular Systems Inc.|Stent fabricated from polymer composite toughened by a dispersed phase|

---

US9091004B2|2006-07-14|2015-07-28|Kimberly-Clark Worldwide, Inc.|Biodegradable polylactic acid for use in nonwoven webs|

---

US7943218B2|2006-08-14|2011-05-17|Frito-Lay North America, Inc.|Environmentally-friendly multi-layer flexible film having barrier properties|

---

JP5383011B2|2006-08-17|2014-01-08|三菱樹脂株式会社|Heat-shrinkable film, molded article using the heat-shrinkable film, heat-shrinkable label, and container using or fitted with the molded article|

---

KR100786005B1|2006-08-18|2007-12-14|에스케이씨 주식회사|Multilayered aliphatic polyester film|

---

US8410215B2|2006-08-23|2013-04-02|Jsr Corporation|Thermoplastic resin composition and molded article obtained from the same|

---

AU2006347731B2|2006-08-31|2012-09-13|Kimberly-Clark Worldwide, Inc.|Highly breathable biodegradable films|

---

JP5233105B2|2006-09-27|2013-07-10|豊田合成株式会社|Polylactic acid resin molded product|

---

US7557167B2|2006-09-28|2009-07-07|Gore Enterprise Holdings, Inc.|Polyester compositions, methods of manufacturing said compositions, and articles made therefrom|

---

JP5145695B2|2006-11-09|2013-02-20|東レ株式会社|Method for producing polylactic acid resin film|

---

CA2672476C|2006-12-14|2013-10-22|Pactiv Corporation|Expanded and extruded biodegradable and reduced emission foams made with methyl formate-based blowing agents|

---

US7977397B2|2006-12-14|2011-07-12|Pactiv Corporation|Polymer blends of biodegradable or bio-based and synthetic polymers and foams thereof|

---

CN101563391B|2006-12-15|2012-04-18|金伯利-克拉克环球有限公司|Biodegradable polylactic acids for use in forming fibers|

---

BRPI0719496B1|2006-12-21|2019-05-14|Dow Global Technologies Inc.|PROCESS TO MAKE A COMPOSITION|

---

CN101535405B|2006-12-22|2012-06-20|尤尼吉可株式会社|Biodegradable polyester resin composition, and molded body, foamed body and molded container obtained from the biodegradable polyester resin composition|

---

CA2667183A1|2006-12-27|2008-07-03|Toray Industries, Inc.|Resin composition and molded article|

---

JP2008163072A|2006-12-27|2008-07-17|Toray Ind Inc|Film containing biodegradable resin|

---

KR101444490B1|2007-02-06|2014-09-24|미쓰비시 쥬시 가부시끼가이샤|Thermally shrinkable film, molded article and thermally shrinkable label both using the thermally shrinkable film, and container using the molded article or having the label attached thereon|

---

US8030382B2|2007-02-23|2011-10-04|Teijin Limited|Polylactic acid composition|

---

EP2500382B1|2007-02-23|2014-09-10|Unitika, Ltd.|Resin composition, and molded article produced from the same|

---

WO2008106631A1|2007-03-01|2008-09-04|Prs Mediterranean Ltd.|Process for producing compatibilized polymer blends|

---

NL1033719C2|2007-04-19|2008-10-21|Synbra Tech Bv|Particulate expandable polylactic acid, method for making it, foamed molded part based on particulate expandable polylactic acid as well as method for making it.|

---

JP5298383B2|2007-04-25|2013-09-25|Ｅｓファイバービジョンズ株式会社|Heat-adhesive conjugate fiber excellent in bulkiness and flexibility and fiber molded article using the same|

---

JP5072077B2|2007-05-21|2012-11-14|三菱樹脂株式会社|Light-shielding heat-shrinkable film, molded product using this light-shielding heat-shrinkable film, heat-shrinkable label, and container using this molded product or attached with this label|

---

US20080311814A1|2007-06-15|2008-12-18|Tredegar Film Products Corporation|Activated bicomponent fibers and nonwoven webs|

---

WO2009012284A1|2007-07-16|2009-01-22|Groupo P.I. Mabe, S.A. De C.V.|Environmentally sensitive diapers manufactured with renewable resources|

---

WO2009032199A1|2007-08-31|2009-03-12|The Board Of Trustees Operating|Beta-cyclodextrins as nucleating agents for poly|

---

US8287677B2|2008-01-31|2012-10-16|Kimberly-Clark Worldwide, Inc.|Printable elastic composite|

---

WO2009100732A1|2008-02-14|2009-08-20|Fiberweb Corovin Gmbh|Bicomponent fibers, textile sheets and use thereof|

---

CN102046704B|2008-03-27|2013-11-20|东丽株式会社|Process for producing thermoplastic resin composition|

---

DE102008022289B4|2008-04-25|2010-07-29|Deutsches Zentrum für Luft- und Raumfahrt e.V.|missile|

---

IT1387503B|2008-05-08|2011-04-13|Novamont Spa|ALYPATIC-AROMATIC BIODEGRADABLE POLYESTER|

---

MX2010013139A|2008-05-30|2011-03-04|Kimberly Clark Worldwide Incorporated|Polylactic acid fibers.|

---

KR100962387B1|2008-06-05|2010-06-10|제일모직주식회사|Polylactic acid resin composition|

---

WO2009151437A1|2008-06-09|2009-12-17|Kimberly-Clark Worldwide, Inc.|Humidification of polylactic acid for fiber formation|

---

WO2009151439A1|2008-06-09|2009-12-17|Kimberly-Clark Worldwide, Inc.|Method for forming biodegradable polylactic acids for use in forming fibers|

---

US8268913B2|2008-06-30|2012-09-18|Fina Technology, Inc.|Polymeric blends and methods of using same|

---

US8642701B2|2008-06-30|2014-02-04|Fina Technology, Inc.|Polypropylene and polylactic acid blends of injection stretch blow molding applications|

---

US8796383B2|2008-06-30|2014-08-05|Fina Technology, Inc.|Polypropylene and polylactic acid formulations for heat seal applications|

---

US8759446B2|2008-06-30|2014-06-24|Fina Technology, Inc.|Compatibilized polypropylene and polylactic acid blends and methods of making and using same|

---

US8530577B2|2008-06-30|2013-09-10|Fina Technology, Inc.|Compatibilized polypropylene heterophasic copolymer and polylactic acid blends for injection molding applications|

---

US8545971B2|2008-06-30|2013-10-01|Fina Technology, Inc.|Polymeric compositions comprising polylactic acid and methods of making and using same|

---

US20110132519A1|2008-06-30|2011-06-09|Fina Technology, Inc.|Polyolefin polylactic acid blends for easy open packaging applications|

---

JP2012504166A|2008-09-29|2012-02-16|ビーエーエスエフソシエタス・ヨーロピア|Biodegradable polymer mixture|

---

US20110245420A1|2008-11-13|2011-10-06|Rasal Rahul M|Copolymer including polylactic acid, acrylic acid and polyethylene glycol and processes for making the same|

---

US20110046281A1|2009-08-19|2011-02-24|Cereplast, Inc.|Polymer compositions having poly|

---

MX2012005237A|2009-11-09|2012-06-13|Basf Se|Method for producing shrink films.|

---

AU2010339869B2|2009-12-17|2014-12-18|3M Innovative Properties Company|Dimensionally stable nonwoven fibrous webs and methods of making and using the same|

---

US8466337B2|2009-12-22|2013-06-18|Kimberly-Clark Worldwide, Inc.|Biodegradable and breathable film|

---

CN102115576B|2009-12-31|2014-09-17|金伯利-克拉克环球有限公司|Natural biological polymer thermoplastic film|

---

US20110251346A1|2010-04-12|2011-10-13|Fina Technology, Inc.|Biodegradable Polymeric Compositions and Methods of Making and Using the Same|

---

US8900698B2|2010-07-30|2014-12-02|Toray Industries, Inc.|Polylactic acid resin sheet and molded article|

---

US20120164905A1|2010-08-13|2012-06-28|Kimberly-Clark Worldwide, Inc.|Modified Polylactic Acid Fibers|

---

US8936740B2|2010-08-13|2015-01-20|Kimberly-Clark Worldwide, Inc.|Modified polylactic acid fibers|

---

US10753023B2|2010-08-13|2020-08-25|Kimberly-Clark Worldwide, Inc.|Toughened polylactic acid fibers|

---

JP2010280921A|2010-09-24|2010-12-16|Toray Ind Inc|White polylactic acid film|

---

US8628718B2|2011-02-18|2014-01-14|Fina Technology, Inc.|Modified polylactic acid, polymeric blends and methods of making the same|

---

US20120214944A1|2011-02-18|2012-08-23|Fina Technology, Inc.|Polyolefin polylactic acid in-situ blends|

---

US8975305B2|2012-02-10|2015-03-10|Kimberly-Clark Worldwide, Inc.|Rigid renewable polyester compositions having a high impact strength and tensile elongation|

---

US20130210621A1|2012-02-10|2013-08-15|Kimberly-Clark Worldwide, Inc.|Breathable Film Formed from a Renewable Polyester|

---

US10858762B2|2012-02-10|2020-12-08|Kimberly-Clark Worldwide, Inc.|Renewable polyester fibers having a low density|

---

US8637130B2|2012-02-10|2014-01-28|Kimberly-Clark Worldwide, Inc.|Molded parts containing a polylactic acid composition|

---

US9040598B2|2012-02-10|2015-05-26|Kimberly-Clark Worldwide, Inc.|Renewable polyester compositions having a low density|US8975305B2|2012-02-10|2015-03-10|Kimberly-Clark Worldwide, Inc.|Rigid renewable polyester compositions having a high impact strength and tensile elongation|

---

US9040598B2|2012-02-10|2015-05-26|Kimberly-Clark Worldwide, Inc.|Renewable polyester compositions having a low density|

---

US20160130413A1|2013-05-23|2016-05-12|Solegear Bioplastics Inc.|Thermoformable polylactic acid|

---

AU2014304179B2|2013-08-09|2017-08-17|Kimberly-Clark Worldwide, Inc.|Anisotropic polymeric material|

---

BR112016002594B1|2013-08-09|2021-08-17|Kimberly-Clark Worldwide, Inc.|METHOD TO SELECTIVELY CONTROL THE DEGREE OF POROSITY IN A POLYMERIC MATERIAL, AND, POLYMERIC MATERIAL|

---

US10946117B2|2013-11-20|2021-03-16|Kimberly-Clark Worldwide, Inc.|Absorbent article containing a soft and durable backsheet|

---

CN106795670A|2013-11-20|2017-05-31|金伯利-克拉克环球有限公司|Soft and durable nonwoven composite|

---

CN107073162A|2014-11-18|2017-08-18|金伯利-克拉克环球有限公司|Soft and durable nonwoven web|

---

GB2549412B8|2014-11-26|2021-07-07|Kimberly Clark Co|Annealed porous polyolefin material|

---

US20170306537A1|2014-11-26|2017-10-26|Kimberly-Clark Worldwide, Inc.|Porous Polyolefin Material Containing a Butene Polymer|

---

US10577494B2|2014-12-22|2020-03-03|3M Innovative Properties Company|Compositions and films comprising polylactic acid polymer, polyvinyl acetate polymer and plasticizer|

---

CN108779370B|2015-12-22|2021-02-12|3M创新有限公司|Packaged pre-adhesive composition, adhesive and article comprising polylactic acid containing packaging material|

---

US11066551B2|2016-05-20|2021-07-20|3M Innovative Properties Company|Oriented polylactic acid polymer based film|

---

US10982090B2|2016-06-21|2021-04-20|3M Innovative Properties Company|Graphic articles comprising polylactic acid polymer based film|

---

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

---

US10662325B2|2017-07-13|2020-05-26|Exxonmobil Chemical Patents Inc.|Polyester compositions, and process for making articles therefrom|

---

US20200198308A1|2018-11-16|2020-06-25|Mucell Extrusion, Llc|Anisotropic thin polyethylene sheet and applications thereof and the process of making the same|

---

CN111718569A|2020-07-09|2020-09-29|上海浦景化工技术股份有限公司|Method for recovering polyglycolic acid and application thereof|

法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-03-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-15| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2021-01-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/01/2013, 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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US13/370,900|2012-02-10|

---

US13/370,900|US8980964B2|2012-02-10|2012-02-10|Renewable polyester film having a low modulus and high tensile elongation|

---

PCT/IB2013/050733|WO2013118023A1|2012-02-10|2013-01-28|Renewable polyester film having a low modulus and high tensile elongation|

---