Biodegradable Thermoplastic Polyester Composition with Improved Wettability

专利摘要:
The present invention relates to aliphatic polyester polymers selected from the group consisting of polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers, or copolymers of these polymers; Multiple carboxylic acids; And an unreacted mixture of humectants. The thermoplastic composition can be extruded as a fiber, which can be formed into a nonwoven structure that can be used in disposable absorbent articles intended for the absorption of fluids such as body fluids.
公开号:KR20010073030A
申请号:KR1020017002507
申请日:1999-08-27
公开日:2001-07-31
发明作者:푸-쟈 차이；브리지트 씨. 워테임
申请人:로날드 디. 맥크레이；킴벌리-클라크 월드와이드, 인크.；
IPC主号:

专利说明:

Biodegradable Thermoplastic Polyester Composition with Improved Wettability}
[2] Disposable absorbent products, which are now widely available, are used in many fields. For example, in the field of infant and child care, reusable fabric absorbent products have generally been replaced by diapers and training pants. Other typical disposable absorbent products are feminine care products such as sanitary napkins or tampons, adult incontinence products, and health care products such as surgical drapes or wound dressings. Typical disposable absorbent articles generally include a topsheet, a backsheet, and a composite structure comprising an absorbent structure interposed between the topsheet and the backsheet. These products typically include some form of fastening system that allows the product to fit the wearer well.
[3] Disposable absorbent products typically come into contact with one or more liquid wastes such as water, urine, menstrual blood or blood during use. Therefore, the outer cover backsheet material of the disposable absorbent article is typically a polypropylene film that retains its shape while being used by the wearer and has sufficient strength and handleability to prevent liquid from leaking out and staining the product. And liquid-insoluble and liquid-impermeable materials such as
[4] While current disposable infant diapers and other disposable absorbent products are generally accepted by the public, these products still have room for improvement in certain areas. For example, many disposable absorbent products are difficult to dispose of. For example, the flow of many disposable absorbent products from a toilet to a sewage treatment system typically blocks the toilet or pipes connecting the toilet and the sewage treatment system. In particular, the outer cover material typically used in disposable absorbent articles generally does not decompose or disperse when spilled into the toilet, so the disposable absorbent articles cannot be disposed of in this way. If the outer cover material is made very thin in order to reduce the overall volume of the disposable absorbent product to reduce clogging of the toilet or sewer pipes, this outer cover material is typically used to reduce the stresses generated during normal use by the wearer. Under stress, you will not have enough strength to prevent tearing or crushing.
[5] Moreover, there is a growing interest in solid waste worldwide. As landfills continue to fill, other methods besides using less resources in disposable products, using more recyclable and / or degradable ingredients in disposable products, and throwing them in solid waste disposal facilities such as landfills It is required to devise a product that can be disposed of.
[6] Accordingly, there is a need for new materials that can be used in disposable absorbent articles that can be disposed of more efficiently after use while still maintaining the shape and strength of the absorbent article during use. For example, such disposable absorbent products can be easily and efficiently disposed of by being rotted and composted. On the one hand, such disposable absorbent products can be easily and efficiently disposed of into a liquid sewage treatment system in which the disposable absorbent products can be broken down.
[7] Many commercially biodegradable polymers are aliphatic polyester materials. Fibers made from aliphatic polyesters are known, but there are problems with using them. In particular, aliphatic polyester polymers are known to have a relatively slower crystallization rate than, for example, polyolefin polymers, which often leads to poor processability of aliphatic polyester polymers. Most aliphatic polyester polymers also have a much lower melting point than polyolefins, making it difficult to cool sufficiently before the thermal processing process. Aliphatic polyester polymers are generally not wettable in nature and need to be modified for use in personal care applications. In addition, the use of processing additives may delay the biodegradation rate of the raw materials, and the processing additives themselves may not be biodegradable.
[8] <Overview of invention>
[9] The present invention preferably relates to a thermoplastic composition which is biodegradable yet easy to manufacture and readily processed into the desired final structure, such as a fiber or nonwoven structure.
[10] One embodiment of the invention relates to a thermoplastic composition comprising a mixture of a first component and a second component and a third component.
[11] One embodiment of such a thermoplastic composition is an aliphatic selected from the group consisting of polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers, or copolymers of these polymers. Polyester polymers; Multiple carboxylic acids having less than about 30 carbon atoms in total; And an unreacted mixture of wetting agents exhibiting a hydrophilic-lipophilic balance ratio of about 10 to about 40, and having the desired properties.
[12] In another embodiment, the present invention relates to a fiber made of said thermoplastic composition, having the desired properties.
[13] In another embodiment, the present invention relates to a nonwoven structure comprising fibers made of the thermoplastic composition.
[14] One embodiment of such a nonwoven structure is a backsheet useful for disposable absorbent articles.
[1] The present invention relates to aliphatic polyester polymers selected from the group consisting of polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers, or copolymers of these polymers; Multicarboxylic acids; And an unreacted mixture of humectants. The thermoplastic composition can be extruded as a fiber, which can be formed into a nonwoven structure that can be used in disposable absorbent articles intended for the absorption of fluids such as body fluids.
[15] The present invention relates to a thermoplastic composition comprising a first component, a second component and a third component. As used herein, "thermoplastic" material refers to a material that softens when exposed to heat and returns to its original state substantially when cooled to room temperature.
[16] It has been found that by using unreacted mixtures of the components described herein, it is possible to produce thermoplastic compositions that are readily processed into fibers and nonwoven structures that are substantially biodegradable and exhibit effective fiber mechanical properties.
[17] The first component of the thermoplastic composition is an aliphatic poly selected from the group consisting of polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers, or copolymers of these polymers. Ester polymer.
[18] Polybutylene succinate polymers are generally prepared by condensation polymerization of glycols with dicarboxylic acids or acid anhydrides thereof. The polybutylene succinate polymer can be a linear polymer or a long chain branched polymer. Long-chain branched polybutylene succinate polymers are generally prepared using additional polyfunctional components selected from the group consisting of trifunctional or tetrafunctional polyols, oxycarboxylic acids and polybasic carboxylic acids. Manufacture. Polybutylene succinate polymers are known in the art and are described, for example, in European patent application 0569 153 A2 of Showa Highpolymer Co., Ltd., Tokyo, Japan.
[19] Polybutylene succinate-co-adipate polymers are generally prepared by the polymerization of one or more alkyl glycols and one or more aliphatic polyfunctional acids. Polybutylene succinate-co-adipate polymers are known in the art.
[20] Examples of polybutylene succinate polymers and polybutylene succinate-co-adipate polymers suitable for use in the present invention include BIONOLLE®, commercially available from Showa High Polymer Company Limited, Tokyo, Japan. Polybutylene succinate-co-adipates and various polybutylene succinate polymers such as 1020 polybutylene succinate polymer or bionole 3020 polybutylene succinate-co-adipate polymers (which are essentially linear polymers) Polymers are included. These materials are known to be substantially biodegradable.
[21] Polycaprolactone polymers are generally prepared by polymerization of ε-caprolactone. Examples of polycaprolactone polymers suitable for use in the present invention include ton (TONE®) polymer P767E and tone polymer P787 polycaprolactone polymers at Union Carbide Corporation, Somerset, NJ. Various polycaprolactone polymers commercially available are included. These materials are known to be substantially biodegradable.
[22] The aliphatic polyester polymers selected from the group consisting of polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers or copolymers of these polymers, It is generally preferred that a thermoplastic composition having the desired properties be present in an amount effective to produce. Based on the total weight of the aliphatic polyester polymer and the polycarboxylic acid and the wetting agent present in the thermoplastic composition, the aliphatic polyester polymer is in the thermoplastic composition greater than 0 to less than 100 weight percent, advantageously about 40 to less than 100 weight percent, more It will advantageously be present in an amount of about 50 to about 95 weight percent, suitably about 60 to about 90 weight percent, more suitably about 60 to about 80 weight percent, most suitably about 70 to about 75 weight percent. .
[23] Aliphatic polyester polymers preferably exhibit an effective weight average molecular weight for thermoplastic compositions having desirable melt strength, fiber mechanical strength, and fiber spinning properties. In general, if the weight average molecular weight of the aliphatic polyester polymer is too large, a thermoplastic composition may be prepared comprising the aliphatic polyester polymer that is difficult to process due to the heavy entangled polymer chains. On the contrary, if the weight average molecular weight of the aliphatic polyester polymer is too small, the polymer chain may not be sufficiently entangled, and thus a thermoplastic composition may be prepared including the aliphatic polyester polymer having a relatively low melt strength and very high speed processing. Thus, aliphatic polyester polymers suitable for use in the present invention advantageously have a weight average molecular weight of about 10,000 to about 2,000,000, more advantageously about 50,000 to about 400,000, suitably about 100,000 to about 300,000. The weight average molecular weight of the polymer or polymer blend can be determined by methods known in the art.
[24] The aliphatic polyester polymer preferably exhibits a polydispersity index value effective for thermoplastic compositions having desirable melt strength, fiber mechanical strength, and fiber spinning. As used herein, "polydispersity index" refers to the weight average molecular weight of a polymer divided by the number average molecular weight of the polymer. The number average molecular weight of the polymer or polymer blend can be determined by methods known in the art. In general, if the polydispersity value of an aliphatic polyester polymer is too large, it is difficult to process during spinning due to inconsistent processability due to polymer fragments containing low molecular weight polymers having lower melt strength. A thermoplastic composition comprising a can be prepared. Thus, the aliphatic polyester polymer advantageously has a polydispersity index value of about 1 to about 15, more advantageously about 1 to about 4, suitably about 1 to about 3.
[25] It is generally preferred that the aliphatic polyester polymer is melt processable. Thus, the aliphatic polyester polymer is advantageously required to have a melt flow rate of about 1 to about 200 g / 10 min, suitably about 10 to about 100 g / 10 min, more suitably about 20 to about 40 g / 10 min. The melt flow rate of the material can be determined according to ASTM test method D 1238-E, which is incorporated herein by reference in its entirety.
[26] In the present invention, the aliphatic polyester polymer is required to be substantially biodegradable. Thus, thermoplastic compositions comprising aliphatic polyester polymers, in the form of fibers or nonwoven structures, will be substantially biodegradable upon disposal or exposure to air and / or water. As used herein, "biodegradable" is a substance that is degraded by the action of naturally occurring microorganisms such as bacteria, fungi and algae. Biodegradability of a material can be determined using ASTM test method 5338.92 or ISO CD test method 14855, which is incorporated by reference in its entirety herein. In one embodiment, a modified ASTM test method 5338.92, which maintains the test chamber at about 58 ° C throughout the test instead of using an incremental temperature profile, can be used to determine the biodegradability of the material.
[27] In the present invention, the aliphatic polyester polymer is required to be substantially compostable. Thus, thermoplastic compositions comprising aliphatic polyester polymers, in the form of fibers or nonwoven structures, will be substantially composted upon disposal or exposure to air and / or water. As used herein, "compostable" is a substance that is biologically decomposed at a rate comparable to known compostable materials so that the material is invisible to the naked eye and decomposed into carbon dioxide, water, inorganic compounds and biomass. Say that.
[28] The second component in the thermoplastic composition is a poly carboxylic acid. Multiple carboxylic acids are any acids comprising two or more carboxylic acid groups. In one embodiment of the invention, the multiple carboxylic acids are preferably linear. Dicarboxylic acids having two carboxylic acid groups are suitable for use in the present invention. In general, the total number of carbons of the polycarboxylic acids is preferably not too high because the rate of crystallization, i.e., the rate at which crystallization of the fibers or nonwoven structures made from the thermoplastic compositions of the present invention, may be slower than desired. The total number of carbon atoms of the multicarboxylic acids is thus advantageously less than about 30, more advantageously from about 4 to about 30, suitably about 5 to about 20, and most suitably about 6 to about 10. Suitable multicarboxylic acids include, but are not limited to, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and mixtures of these acids.
[29] In general, the multiple carboxylic acids should be present in the thermoplastic composition in an amount effective to produce a thermoplastic composition having the desired properties. Based on the total weight of the aliphatic polyester polymer and the polycarboxylic acid and the wetting agent present in the thermoplastic composition, the polycarboxylic acid is present in an amount greater than 0% by weight, advantageously greater than 0 to about 30% by weight, more advantageously about It will be present in an amount from 1 to about 30 weight percent, suitably about 5 to about 25 weight percent, more suitably about 5 to about 20 weight percent, and most suitably about 5 to about 15 weight percent.
[30] In order to process the thermoplastic composition of the invention into an article such as a fiber or nonwoven structure exhibiting the properties required by the invention, the polycarboxylic acid is preferably present in the liquid state during the thermal processing of the thermoplastic composition so that the processed thermoplastic composition is While cooling, it has been found that it is generally desirable for the polycarboxylic acid to become solid or crystallized before the aliphatic polyester polymer becomes solid or crystallized.
[31] Multiple carboxylic acids in the thermoplastic compositions of the present invention are believed to perform two important but different functions. First, when the thermoplastic composition is in the molten state, the polycarboxylic acid, through the internal modification of the aliphatic polyester polymer, increases the flexibility and toughness of the final product, such as a fiber or nonwoven structure, while making the processing lubricant easier to process the thermoplastic composition. Or as a plasticizer. While not intending to conclude this, the polycarboxylic acid is thought to facilitate the transfer of polymer chain fragments by replacing the secondary valence bonds that hold the aliphatic polyester polymer chains together with the valence bonds of the polycarboxylic acid and aliphatic polyester polymers. do. As a result, the torque required to operate the extruder is generally markedly reduced compared to the processing of aliphatic polyester polymers alone. In addition, the processing temperature required to spin the thermoplastic composition into a final product, such as a fiber or nonwoven structure, is generally significantly reduced, which not only reduces the risk of thermal decomposition of the aliphatic polyester polymer, but also requires the manufacture of any fiber or nonwoven structure. Amount and cooling rate are reduced. Second, when the final product made of a thermoplastic composition, such as a fiber or nonwoven structure, is cooled and solidified from its liquid or molten state, it is believed that the multicarboxylic acid performs the function as a nucleating agent. Aliphatic polyester polymers are known to have very slow crystallization rates. Typically, there are two important ways to solve this problem. One is to change the cooling temperature profile to maximize the rate of crystallization, and the other is to add a nucleating agent that increases the crystallization site and degree.
[32] The process of cooling the extruded polymer to room temperature typically involves blowing air onto the extruded polymer at room temperature or sub-ambient temperature slightly below room temperature. This process can be referred to as quenching or super-cooling because the change in temperature over a relatively short period of time (in seconds) is at least 100 ° C. and most often at least 150 ° C. By reducing the melt viscosity of the polymer, it is generally possible to successfully extrude the polymer at lower temperatures. This generally reduces the temperature change required during cooling advantageously below 150 ° C., and in some cases below 100 ° C. It is very difficult to convert this conventional process into the ideal cooling temperature profile required to make the single process maximize the crystallization rate of the aliphatic polyester in the actual manufacturing process, because extreme cooling is required in a very short time. However, standard cooling methods can be used in combination with the second variant method. A typical second method is to mix a nucleating agent, such as a solid particulate material, with the thermoplastic composition to provide a crystallization initiation site during quenching. However, such solid nucleating agents generally agglomerate very easily in thermoplastic compositions, which may cause clogging of the filter and spinneret holes during spinning. In addition, the nucleation effect of such a solid nucleating agent is typically maximized when the amount of the solid nucleating agent added is about 1%. Because of these two factors, it is generally not possible to add or need to add many weight percent of the solid nucleating agent to the thermoplastic composition. However, in processing the thermoplastic compositions of the present invention, it has been found that polycarboxylic acids generally exist in the liquid state during the extrusion process and act as plasticizers, while during cooling they still solidify or crystallize before the aliphatic polyester to act as nucleating agents. lost. When multiple carboxylic acids are cooled from a homogeneous melt, they are considered to be relatively quick and fully solidify or crystallize when they fall below their melting point because they are relatively small molecules. For example, the adipic acid has a melting point of about 162 ° C and a crystallization temperature of about 145 ° C.
[33] The macromolecular aliphatic polyester polymers have a relatively very slow crystallization rate, which generally means that when the aliphatic polyester polymer cools, it solidifies or crystallizes more slowly at temperatures below its melting point. During this cooling, the multiple carboxylic acids begin to crystallize before the aliphatic polyester polymer and generally act as solid nucleation sites in the cooled thermoplastic composition.
[34] Another important challenge encountered in thermally processing aliphatic polyester polymers into fibers or nonwoven structures is the sticky nature of such polymers. Drawing fibers by mechanical or air drawing processes often causes the fibers to agglomerate, resulting in a solid mass. In general, it is known that the addition of solid fillers reduces the stickiness of the polymer melt in most cases. However, the use of solid fillers in fiber spinning or nonwoven devices where the polymer is extruded through holes with very small diameters can be problematic. This is because filler particles can block the spinneret and the filter screen, which can interfere with the fiber spinning process. In the present invention, on the contrary, the multiple carboxylic acids generally solidify during the quenching process while in the liquid state during the extrusion process. Thus, multiple carboxylic acids effectively act as solid fillers to improve the total crystallinity of the system, reduce the stickiness of the fibers and solve problems such as fiber aggregation during stretching.
[35] Multiple carboxylic acids must be very chemically miscible with aliphatic polyester polymers mixed together. While the prior art generally says that polylactide-adipic acid mixtures can be used, unique combinations have been found in the present invention. Polylactide-adipic acid mixtures are generally mixed with relatively small amounts of wetting agents, for example less than about 2% by weight, but with very difficult problems. Polybutylene succinate, polybutylene succinate-co-adipate and polycaprolactone have been found to be very miscible with both large amounts of multiple carboxylic acids and wetting agents. The reason is considered to be due to the chemical structure of the aliphatic polyester polymer. Polylactide polymers have a relatively bulky chemical structure that does not have a linear portion longer than CH ₂ . In other words, each CH ₂ fragment is bonded to carbon with oxygen or other side chains. Thus, multiple carboxylic acids, such as adipic acid, cannot be aligned close to the polylactide polymer backbone. In the case of polybutylene succinate and polybutylene succinate-co-adipate, the polymer backbone has repeating units (CH ₂ ) ₂ and (CH ₂ ) ₄ in its structure. Polycaprolactone has a repeating unit (CH ₂ ) ₅ . These relatively long, open and linear moieties, unhindered by oxygen atoms and bulky side chains, are well aligned with suitable polycarboxylic acids, such as adipic acid with (CH ₂ ) ₄ , such that the polycarboxylic acid and suitable aliphatic poly The ester polymer molecules are in very close contact. Due to the excellent miscibility of these polycarboxylic acids and aliphatic polyester polymers, the third component of the present invention, the wetting agent, can be used relatively easily. Such suitable miscibility can be achieved by mixing polybutylene succinate, polybutylene succinate-co-adipate, polycaprolactone, or a blend or copolymer of these polymers with a mixture of suitable polycarboxylic acids and wetting agents or by fibres or nonwovens. It is also proven by the fact that it is easy to manufacture into a structure. The processability of such mixtures is excellent, but in the case of polylactide-polycarboxylic acid systems, wetting agents are generally not easily added to the mixture.
[36] Polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers or copolymers of these polymers, when used alone or in combination, are generally hydrophobic to be. Since the thermoplastic composition of the present invention, and the fiber or nonwoven structure made from the thermoplastic composition, should generally be hydrophilic, it is necessary to add another component to the thermoplastic composition of the present invention to obtain the desired properties. Thus, the thermoplastic composition of the present invention comprises a humectant.
[37] Accordingly, the third component in the thermoplastic composition is for polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers and / or copolymers of these polymers. Wetting agent. Generally wetting agents suitable for use in the present invention are generally hydrophilic sites of polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers or copolymers of these polymers. Hydrophobicity that is miscible with hydrophilic sites that are miscible with and generally polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers or copolymers of these polymers Will contain the site. The hydrophilic and hydrophobic sites of the humectant will generally be in different blocks so that the overall humectant structure will be a di-block or a random block. Wetting agents having a melting point lower than or slightly above the melting point of the aliphatic polyester polymer are preferred because during quenching the wetting agent must be present as a liquid even after the aliphatic polyester polymer has crystallized. This generally causes the wetting agent to migrate to the surface of the fabricated fibrous structure to improve the wettability and processability of the fibrous structure. In general, wetting agents are required to act as surfactants in materials processed from thermoplastic compositions, such as fibers or nonwoven structures, to change the contact angle of water in the air of the processed materials. The hydrophobic moiety of the wetting agent may be, but is not limited to, a polyolefin such as polyethylene or polypropylene. The hydrophilic moiety of the humectant may contain ethylene oxide, ethoxylate, glycol, alcohol or any combination thereof. Examples of suitable humectants include UNITHOX® 480 from the Petrolite Corporation, Tulsa, Oklahoma, USA, and UNICID® from the Unitox 750 ethoxylated alcohol or petroleum corporation. Trademarks) acid amide ethoxylates.
[38] Other suitable surfactants include, for example, one or more of the following: (1) consisting of silicone glycol copolymers, such as D193 and D1315 silicone glycol copolymers available from Dow Corning Corporation, Midland, Mich. Surfactants; (2) GENAPOL® 24-L-60, Xenapol 24-L-92 or Xenapol 24-L, available from Hoechst Celanese Corp., Charlotte, North Carolina, USA Ethoxylated alcohols, such as -98N ethoxylated alcohol; (3) Ethoxylated mono- and diglycerides, such as MAZOL® 80 MGK ethoxylated diglycerides, commercially available from PPG Industries, Inc., Journey, Illinois. Surfactant consisting of; (4) Carboxylic alcohol ethoxylates such as SANDOPAN (R) DTC, pH Plate KST, or Acid Plate DTC-100 Carboxylated Alcohol Ethoxylate, available from Sandoz Chemical Corp. Surfactant consisting of; (5) Ethoxylated fatty esters, such as TRYLON® 5906 and Triron 5909 ethoxylated fatty esters available from Henkel Corp./Emery Grp., Cincinnati, Ohio, USA .
[39] Wetting agents should have a weight average molecular weight effective for thermoplastic compositions having desirable melt strength, fiber mechanical strength, and fiber spinning. In general, if the weight average molecular weight of the wetting agent is too large, the viscosity of the wetting agent will be so high that it will lose the fluidity required for blending and the wetting agent will not blend well with other components in the thermoplastic composition. In contrast, if the weight average molecular weight of the humectant is too small, the humectant will generally not blend very well with other ingredients and will have a viscosity low enough to cause processing problems. Accordingly, wetting agents suitable for use in the present invention advantageously have a weight average molecular weight of about 1,000 to about 100,000, suitably about 1,000 to about 50,000, more suitably about 1,000 to about 10,000. The weight average molecular weight of the wetting agent can be determined by methods known in the art.
[40] In general, wetting agents are required to have an effective hydrophilic-lipophilic balance ratio (HLB ratio). The HLB ratio of a substance is the relative ratio of the hydrophilicity of the substance. The HLB ratio is obtained by dividing the weight average molecular weight of the hydrophilic site by the total weight average molecular weight of the substance and multiplying by 20. If the HLB ratio is too small, the humectant generally does not provide the desired hydrophilicity improvement effect. In contrast, if the HLB ratio is too large, wetting agents are generally difficult to blend into the thermoplastic composition due to chemical incompatibility and viscosity differences with other components. Thus, wetting agents useful in the present invention advantageously have an HLB ratio of about 10 to about 40, suitably about 10 to about 20, more suitably about 12 to about 16. The HLB ratio of certain wetting agents is generally known and / or can be obtained by various known methods.
[41] In general, the hydrophobic moiety of the humectant should be a linear hydrocarbon chain containing (CH ₂ ) _n , where n is preferably at least 4. These linear hydrocarbon hydrophobic sites are generally highly miscible with polybutylene succinate, polybutylene succinate-co-adipate, and polycaprolactone polymers as well as similar sites in many polycarboxylic acids such as adipic acid. If this structural similarity is utilized well, the hydrophobic sites of the humectant will bind very closely to the aliphatic polyester polymer, while the hydrophilic sites will extend to the surface of the fabric or nonwoven structure produced. As a result of this phenomenon, the advancing contact angle exerted by the fabric or nonwoven structure produced is relatively much reduced. Examples of suitable humectants include Unitox 480 and Unitox 750 ethoxylated alcohols available from Petrol Corporation, Tulsa, Oklahoma, USA. Such wetting agents have a linear hydrocarbon chain with an average of 26 to 50 carbons. If the hydrophobic portion of the humectant is too large, such as a phenyl ring or a bulky side chain, the humectant is generally poorly incorporated into the aliphatic polyester polymer blend. The hydrophobic portion of this humectant is not bound to the aliphatic polyester polymer molecule, and the hydrophilic portion of the humectant is freely suspended so that the entire molecule of the humectant floats freely in the mixture and then enters the blend. This is evidenced by the large forward contact angle and the relatively small recessed contact angle, indicating that the hydrophilic chain is absent on the surface. After the liquid dirt flows out, the humectant may migrate to the surface to achieve a small backward contact angle. This is evident from the IGEPAL® RC-630 ethoxylated alkyl phenol surfactants available from Rhone-Poulenc, Cranbury, NJ. IEPAL RC-630 ethoxylated alkyl phenols have bulky phenolic groups that limit the miscibility to aliphatic polyester polymers, which are large forward contact angles and small backwards of the mixture of aliphatic polyester polymers and EEPAL RC-630 ethoxylated alkyl phenols. It can be seen from the angle.
[42] In general, the humectant should be present in the thermoplastic composition in an amount effective to produce a thermoplastic composition having desirable properties such as the desired contact angle value. In general, using too much humectant may cause problems in the processing of the thermoplastic composition, or the final thermoplastic composition may not exhibit desirable properties such as the desired forward and reverse contact angles. The total weight of the polybutylene succinate polymer, polybutylene succinate-co-adipate polymer, polycaprolactone polymer, mixtures of these polymers, or copolymers of these polymers with multiple carboxylic acids and wetting agents, present in the thermoplastic composition On the basis, the humectant is advantageously in the thermoplastic composition, more than 0 to about 25 weight percent, more advantageously about 0.5 to about 20 weight percent, suitably about 1 to about 20 weight percent, more suitably about 1 to about It will be present in an amount of about 15% by weight.
[43] While the main components of the thermoplastic composition of the present invention have been described so far, such thermoplastic compositions are not limited to this, but may also include other components that do not adversely affect the desired properties of the thermoplastic composition. Examples of materials that can be used as additive ingredients include, for example, the processability of pigments, antioxidants, stabilizers, surfactants, waxes, flow promoters, solid solvents, plasticizers, nucleating agents, particulates, and thermoplastic compositions. Other substances that enhance, but are not limited to. When such additive components are included in the thermoplastic composition, polybutylene succinate polymers, polybutylene succinate-co-adipate polymers, polycaprolactone polymers, mixtures of these polymers or these polymers present in the thermoplastic composition Based on the total weight of the copolymer and the polycarboxylic acid and the humectant, the additive components are preferably used in an amount of less than about 10% by weight, more advantageously less than about 5% by weight, and suitably less than about 1% by weight. Do.
[44] The thermoplastic compositions of the invention are generally simple mixtures of aliphatic polyester polymers, polycarboxylic acids, wetting agents, and optionally optional additives. In order to obtain the desirable properties of the thermoplastic composition of the present invention, a copolymer comprising an aliphatic polyester polymer, a polycarboxylic acid and / or a humectant may be present in a state where the aliphatic polyester polymer, the polycarboxylic acid and the humectant are not substantially reacted with each other. It turns out that it is very important that not be formed. Thus, the aliphatic polyester polymer, the polycarboxylic acid and the wetting agent are each individual components of the thermoplastic composition.
[45] In one embodiment of the present invention, the aliphatic polyester polymer, the polycarboxylic acid and the wetting agent are dry mixed together to obtain a thermoplastic composition dry mixture, which is agitated, agitated or otherwise blended in an advantageous manner to form an aliphatic The polyester polymer, the multiple carboxylic acids, and the wetting agent are effectively and uniformly mixed to obtain an essentially homogeneous dry mixture. This dry mixture is then melt blended, for example in an extruder, to effectively and uniformly mix the aliphatic polyester polymer with the polycarboxylic acid and the humectant to obtain an essentially homogeneous melt mixture. This essentially homogeneous melt mixture can be cooled and pelletized. Alternatively, this essentially homogeneous melt mixture may be sent directly to a spin pack or another device for the formation of a fiber or nonwoven structure.
[46] Another method of mixing the components of the present invention is the addition of multiple carboxylic acids and wetting agents to the aliphatic polyester polymer, for example in an extruder used for mixing the components. In addition, there is a method of melt mixing all components simultaneously from the beginning. Other methods of mixing the components of the present invention are possible and will be readily apparent to those skilled in the art. In order to determine whether the aliphatic polyester polymer, the polycarboxylic acid and the humectant are in an essentially unreacted state, techniques such as nuclear magnetic resonance and infrared spectroscopy can be used to evaluate the chemical properties of the final thermoplastic composition.
[47] Typical thermal processing conditions for the various components include advantageously shear rates of about 100 to about 50,000 seconds ⁻¹ , more advantageously about 500 to about 5,000 seconds ⁻¹ , suitably about 1,000 to about 3,000 seconds ^−1. Most suitably about 1000 seconds ^-1 . Typical of the thermal processing conditions of the components include that the temperature is advantageously from about 50 to about 500 ° C, more advantageously from about 75 to about 300 ° C, suitably from about 100 to about 250 ° C.
[48] As used herein, the term "hydrophobic" refers to a contact angle of water in the air of a substance that is at least 90 degrees. In contrast, the term "hydrophilic" refers to the contact angle of water in the air of a substance of less than 90 degrees. However, for commercial personal care products, in general, the contact angle must be much smaller than 90 degrees to provide the desired liquid delivery properties. In order to achieve the fast absorption and wetting properties required for personal care products, the contact angle of water in the air should generally fall below about 70 degrees. In general, the smaller the contact angle, the better the wettability. For this purpose, the contact angle is determined by the method described in the "test method" herein. General information on contact angles and methods of measurement can be found in the art, for example, by Robert J. Good and Robert J. Stromberg, Ed., In “Surface and Colloid Science -Experimental Methods ", Vol. II, (Plenum Press, 1979).
[49] Multicomponent fibers or nonwoven structures of the present invention should exhibit an improvement in hydrophilicity, evidenced by a reduction in the contact angle of water in the air. The contact angle of the water in the air of the fiber sample can be measured as a forward or backward contact angle value by the nature of the test method. The forward contact angle is a measure of how the material initially responds to liquids such as water. The backward contact angle is a measure of how the material reacts when the liquid is first discharged, or when exposed to the liquid, and then when the liquid continues to be discharged. The smaller backward contact angle means that the material is more hydrophilic during liquid exposure and generally can deliver the liquid more consistently. In order to achieve high hydrophilicity of the multicomponent fiber or nonwoven structure of the present invention, both forward and backward contact angle values are used.
[50] Multicomponent fibers or nonwoven structures of the present invention should exhibit an improvement in liquid delivery rate, evidenced by small contact angle hysteresis. As used herein, "contact angle hysteresis" is defined as the difference between the forward and backward contact angles of an evaluation material. For example, a relatively large forward contact angle and a relatively small backward contact angle will achieve large contact angle hysteresis. In this case, although the initial liquid dirt is generally absorbed slowly by the material, the material will generally attempt to retain the liquid once absorbed. In general, to achieve high liquid delivery rates, in addition to the relatively small forward and backward contact angles, small contact angle hysteresis is required. Contact angle hysteresis also indicates the rate of wicking of the liquid on the evaluation material.
[51] In one embodiment of the present invention, the forward contact angle value of a multicomponent fiber or nonwoven structure made from the thermoplastic compositions described herein is advantageously about 70 degrees, measured by the method described in the "Test Methods" herein. Should be less than, more advantageously less than about 65 degrees, suitably less than about 60 degrees, more suitably less than about 55 degrees, most suitably less than about 50 degrees.
[52] In another embodiment of the present invention, the reverse contact angle value of a multicomponent fiber or nonwoven structure made from the thermoplastic compositions described herein is advantageously about 60, as measured by the method described in the "Test Methods" herein. It should be less than degrees, more advantageously less than about 55 degrees, suitably less than about 50 degrees, more suitably less than about 45 degrees, most suitably less than about 40 degrees.
[53] In another embodiment of the invention, the forward contact angle value of a multicomponent fiber or nonwoven structure made from the thermoplastic compositions described herein is a fiber made from a thermoplastic composition that is substantially all the same except that it does not contain a humectant. Or less than about 10 degrees, more advantageously about 15 degrees, suitably about 20 degrees, and more suitably about 25 degrees, advantageously, than the forward contact angle of the nonwoven structure.
[54] In another embodiment of the invention, the reverse contact angle value of a multicomponent fiber or nonwoven structure made from the thermoplastic compositions described herein is a fiber made from a substantially identical thermoplastic composition except that it does not include a humectant. Or less than about 5 degrees, more advantageously about 10 degrees, suitably about 15 degrees, and more suitably about 20 degrees, advantageously, than the reverse contact angle of the nonwoven structure.
[55] As used herein, “fibers or nonwoven structures made from thermoplastic compositions that are all substantially the same except that they do not include a wetting agent” and other similar terms are substantially the same as materials that are substantially the same as the fibers or nonwoven structures of the present invention. Refers to a control fiber or nonwoven structure prepared by the method, which is prepared with or without the wetting agent described herein.
[56] In another embodiment of the present invention, the difference between the forward and backward contact angle values, referred to herein as contact angle hysteresis, is preferably as small as possible. Thus, the difference between the forward and backward contact angle values of the multicomponent fiber is advantageously less than about 50 degrees, more advantageously less than about 40 degrees, suitably less than about 30 degrees, more suitably about 20 degrees. It is required to be less than degrees.
[57] The melting point or softening point of the thermoplastic composition should be within the temperature ranges typically encountered in most processes. Accordingly, the melting or softening point of the thermoplastic composition is advantageously required to be about 25 to about 350 ° C, more advantageously about 35 to about 300 ° C, suitably about 45 to about 250 ° C.
[58] Thermoplastic compositions of the present invention have generally been found to have improved processability over thermoplastic compositions comprising aliphatic polyester polymers but without multiple carboxylic acids and / or wetting agents. This is generally due to the significant decrease in viscosity due to multiple carboxylic acids and the internal lubricating effect of the wetting agent. In the absence of multiple carboxylic acids, the viscosity of the mixture of aliphatic polyester polymer and wetting agent is generally high enough to be unsuitable for processing. Without humectants, mixtures of aliphatic polyester polymers and polycarboxylic acids will generally not be sufficiently hydrophilic and generally will not have the processing advantages of liquid humectants in the quench zone. As part of the present invention, it has been found that the proper combination of these three components yields the proper viscosity and melt strength required for fiber spinning.
[59] As used herein, the degree of improvement in processability of a thermoplastic composition is measured as a decrease in the apparent viscosity of the thermoplastic composition at a temperature of about 170 ° C., which is typical industrial extrusion processing conditions, and a shear rate of about 1,000 seconds ⁻¹ . If the thermoplastic composition exhibits too high an apparent viscosity, this thermoplastic composition will generally be very difficult to process. In contrast, if the thermoplastic composition exhibits too low an apparent viscosity, the thermoplastic composition will generally produce extruded fibers with very poor tensile strength.
[60] Thus, the thermoplastic composition advantageously has a temperature of about 170 ° C. and a shear rate of about 1,000 seconds ⁻¹ , advantageously from about 5 to about 200 Pascal seconds, more advantageously from about 10 to about 150 Pa · s, Suitably should have an apparent viscosity of about 20 to about 100 Pa · s. The method of determining the apparent viscosity value will be described below in connection with the examples.
[61] As used herein, "fiber" or "fibrous" refers to a material having a length to diameter ratio of greater than about 10. In contrast, "nonfiber" or "nonfibrous" refers to a material having a length to diameter ratio of about 10 or less.
[62] Methods of making the fibers are well known and need not be described in detail here. Melt spinning of polymers includes the manufacture of continuous filaments, such as spunbond or meltblown, and discontinuous filaments, such as staple and short-cut fibers or structures do. To produce spunbond or meltblown fibers, the thermoplastic composition must generally be extruded and placed in a dispensing system where the thermoplastic composition is introduced into a spinneret plate. The spun fibers are then cooled, solidified, drawn by an aerodynamic system and formed into conventional nonwovens. On the other hand, to produce cut or staple fibers, the spun fibers are cooled, solidified, drawn to median filament diameters, generally by mechanical roll systems, and collected rather than directly formed into a nonwoven structure. The collected fibers are then "cold drawn" to the desired final fiber diameter at temperatures below their softening point, crimped (texturizing) and cut to the desired fiber length. The fibers can be cut into relatively short lengths, such as staple fibers, generally about 25 to about 50 mm in length, and shorter fibers, generally shorter than about 18 mm in length.
[63] Thermoplastic compositions of the invention include disposable absorbent articles such as diapers, adult incontinence products, and bed pads; Sanitary articles such as sanitary napkins and tampons; And textile or nonwoven structures that can be used in disposable absorbent articles, including handkerchiefs, bibs, wound dressings, and other absorbent articles such as surgical capes or drapes. Thus, in another embodiment, the present invention relates to a disposable absorbent article comprising the multicomponent fiber of the present invention.
[64] In one embodiment of the invention, the thermoplastic composition is formed from a fibrous matrix for use in disposable absorbent articles. The fibrous matrix may take the form of a fibrous nonwoven web, for example. The fibrous nonwoven web may be made only of the fiber made from the thermoplastic composition of the present invention, or may be blended with other fibers. The length of the fibers used may vary depending on the particular end use. If the fibers are to be degraded in water, for example in a toilet, the length is preferably kept below about 15 mm.
[65] In one embodiment of the invention, a liquid-permeable topsheet, the backsheet comprising fibers made from the thermoplastic composition of the invention attached to the liquid-permeable topsheet, and positioned between the liquid-permeable topsheet and the backsheet. A disposable absorbent article is provided that includes an absorbent structure.
[66] Examples of disposable absorbent articles are generally described in US-A-4,710,187; US-A-4,762,521; US-A-4,770,656; And US-A-4,798,603.
[67] Absorbent articles and absorbent structures according to all embodiments of the present invention are generally applied to large amounts of body fluid waste during use. Thus, the absorbent article and the absorbent structure should preferably be able to absorb the body fluid in an amount that is exposed during use. Dirt is usually secreted separately from one another over a period of time.
[68] <Test method>
[69] Melting point
[70] The melting point of the material is determined using differential scanning calorimetry. The differential scanning calorimeter used to determine the melting point was used by TA Instruments Inc. of Newcastle, Delaware, USA, under the trade name Thermal Analyst 2910 Differential Scanning Calorimeter (DSC). Commercially available), equipped with a liquid nitrogen cooling device and using a Thermal Analyst 2200 analysis software program.
[71] The material samples tested are in the form of fiber or resin pellets. Since nothing that can produce erroneous results should be involved, it is preferable to use tweezers or other tools rather than hand-handling the material sample. If the material sample is a fiber it is cut and if it is a resin pellet it is placed in an aluminum pan and weighed on an analytical balance with an accuracy of 0.01 mg. In some cases, a sample of material on the pan is covered with a lid.
[72] Calibrate the differential scanning calorimeter and calibrate the baseline using an indium metal standard as described in the instructions for the differential scanning calorimeter. A sample of material is placed in a test chamber of a differential scanning calorimeter for testing, and an empty pan is used as a reference. All tests are performed while purging with 55 cm 3 / min nitrogen (industrial grade) in the test chamber. The heating and cooling program incubated the chamber at -20 ° C, then heated to 220 ° C at 20 ° C / min, cooled to -20 ° C at 20 ° C / min, and then to 220 ° C at 20 ° C / min. This is a two cycle test.
[73] The results are evaluated using an analysis software program that identifies and quantifies endothermic and exothermic peaks.
[74] Apparent viscosity
[75] The brand name Gottfert Leograph 2003 (Gottfert Co., Ltd.) using the WinRHEO (version 2.31) analysis software available from the Gottfert Company, Rock Hill, SC, USA. Gottfert Rheograph 2003) The apparent viscosity rheological properties of material samples are assessed using commercially available capillary rheometers as capillary rheometers. The capillary rheometer is set up with a 2000 bar (200 MPa) pressure transducer and a 30 mm length / 30 mm active length / 1 mm diameter / 0 mm height / 180 ° angle round hole capillary die do.
[76] If the tested material sample exhibits or is known to exhibit water sensitivity, then in a vacuum oven at a temperature above the glass transition temperature of the material sample, ie, above 55 or 60 ° C. for poly (lactic acid) material. The material sample is dried for at least 16 hours, purging at least 30 standard ft ³ / h (about 0.850 m ³ / h) of nitrogen gas in a vacuum of at least 15 inHg (381 mmHg).
[77] Once the device is warmed up and the pressure transducer is calibrated, the material sample is progressively placed in the column and the polymer resin pellets are filled in a column with ramrods to keep the melt consistent during the test. After loading the material sample, the material sample is melted for 4 minutes in advance before each test so that the material sample can be completely melted at the test temperature. The capillary rheometer automatically takes the data and determines the apparent viscosity (Pa · s) at seven apparent shear rates (s ⁻¹ ) (50, 100, 200, 500, 1000, 2000 and 5000). When examining the curve thus obtained, it is important that the curve should be relatively smooth. If there is significant deviation from the general curve from one point to another due to the air in the column, the test should be repeated to ensure reliable results.
[78] The rheological curve of apparent shear rate versus apparent viscosity obtained in this way shows how the material sample behaves at each temperature during the extrusion process. The apparent viscosity values at temperatures of about 170 ° C. and shear rates of about 1000 s ⁻¹ are particularly important because they are typical conditions found in industrial fiber spinning extruders.
[79] Contact angle
[80] The device consists of a DCA-322 Dynamic Contact Angle Analyzer and WinDCA (version 1.02) software available from ATI-CAHN Instruments, Inc., Madison, WI. . The test is carried out in an "A" loop equipped with a balance stirrup. Before starting the measurement as described in the instructions, the balance of the contact angle analyzer, which can weigh 100 mg, must be calibrated. According to the instructions, the motor must also be calibrated periodically.
[81] The thermoplastic composition is spun into fibers and a free-fall sample (jetstretch 0) is used for contact angle determination. Throughout the fiber manufacturing process, care should be taken to minimize fiber handling by hand to minimize contamination. The fiber sample is attached to a wire hanger with scotch tape so that 2-3 cm of fiber extends past the end of the hanger. The hanger consists of a 4 cm straight wire that is bent at about 0.8 cm from each end and has hooks at its ends. The fiber sample is then cut with a razor to extend 1.5 cm past the end of the hanger. The average diameter of the fibers is determined (3-4 measurements) using an optical microscope such as Leica Galen III manufactured by Leica, Inc., Buffalo, NY, USA. .
[82] The sample on the wire hanger is suspended by a balance stub on the "A" loop of the contact angle analyzer. The dipping solution is distilled water and replace it for each sample. Enter the scales of the sample (eg fiber diameter) and start the test. The stage is advanced to 151.75 microns / second until immersion depth 0 is sensed, when the fiber contacts the surface of distilled water. From immersion depth 0, the fibers are advanced 1 cm into water, stopped for about 0 seconds, and then immediately 1 cm back. The contact angle is automatically analyzed by the software, and the forward and backward angles of the fiber sample are determined based on standard calculations as specified in the instructions. A contact angle of zero or less means that the sample is completely wet. The same test is performed five times for each sample and statistical analysis values such as mean, standard deviation and coefficient of variation percent are calculated. By "advanced contact angle value" recorded in the Examples herein and used in the claims, it means the forward contact angle of distilled water for a test sample, determined according to the test method described above. Similarly, the "reverse contact angle value" recorded in the examples herein and used in the claims means the reverse contact angle of distilled water for a test sample, determined according to the test method described above. Contact angle hysteresis is defined as the difference between the forward and backward contact angles. All values reported herein are mean values determined based on five identical measurements.
[83] Nonwoven Tensile Test
[84] Tensile properties of nonwoven webs were developed by MTS Systems Corporation using Testworks 3.03 analysis software, available from MTS Systems Corporation, Eden Prairie, Minnesota, USA. Measure on D model (Sintech 1 / D Model). One set of 10N pneumatic tensile grips is purchased from MTS (MTS model number 00.01659) and covered with a rubber grip sheath (MTS model number 38.00401). The test uses a 50 lb (about 200 N) load gauge and attaches a rubber-enclosed air-operated grip to the machine. Power on both the load meter and load frame and allow the unit to warm up and stabilize for 30 minutes. The test grip is then moved by hand so that there is a 3 in. (7.62 cm) gap between the upper grip and the lower grip when measured with a ruler and level. The distance is then zeroed on the test software. Open the grip and calibrate the load meter.
[85] The sample is cut into strips 1 inch (2.54 cm) wide and the sample is placed perpendicular to the grip so that no tensile force is applied on the sample. Start the test using software, move the upper grip at a speed of 12.0 in / min (30.48 cm / min) and leave the lower grip stationary. If the nonwoven is broken, finish the test and return the upper grip to his starting point. The software then obtains the measured and calculated values of the sample. Particularly important information is the maximum load, break load and quantity measured directly by the machine. The maximum load is the maximum load obtained at any point during the test and is measured in g. The breaking load is the load at which the sample breaks and is measured in g.
[86] Cup crush test
[87] Cup fracture testing is measured on a new Tech 1 / D model sold by MT Systems Corporation using TestWork 3.03 analysis software available from MT Systems Corporation, Eden Prairie, Minnesota, USA. In this test, a 10 N (approximately 50 N) load gauge is attached to the Syntec frame. A molding cylinder is attached to the bottom and a 6 inch (15.24 cm) x 6 inch (15.24 cm) square shaped nonwoven is covered at the inlet of the cylinder. The forming cup is placed on this nonwoven and forms a nonwoven on the cylinder, exposing an open circle of web on the cylinder. The foot of the cup crusher consists of a metal rod with a circular end and is attached to a 10 lb load gauge. At the start of the test, the foot descends and bumps against the nonwoven web at a rate of 409.40 mm / min. Syntec then measures the maximum load and energy required to break the nonwovens. The foot descended and stopped a total of 62 mm and returned to his original position in the opposite direction. In general, a small maximum load means that the nonwoven is soft.
[88] In the following examples various materials were used to make thermoplastic compositions and multicomponent fibers. The trade names and various properties of these materials are listed in Table 1.
[89] The poly (lactic acid) (PLA) polymer was a trademark HEPLON® A10005 poly (lactic acid) polymer available from Chronopol Inc., Goldden, CO. In Table 2a the heflon A10005 poly (lactic acid) polymer is designated as heflon.
[90] The polybutylene succinate polymer sold under the trade name Bionole 1020 polybutylene succinate was used at Showa High Polymer Company Limited, Tokyo, Japan. In Table 2a the bionole 1020 polybutylene succinate polymer is designated PBS.
[91] A polybutylene succinate-co-adipate polymer sold under the trade name Bionole 3020 polybutylene succinate-co-adipate was used at Showa High Polymer Company Limited, Tokyo, Japan. In Table 2a the bionole 3020 polybutylene succinate-co-adipate polymer is designated PBSA.
[92] A polycaprolactone polymer commercially available from Union Carbide Chemicals and Plastics Co., Ltd. as trade name tone polymer P767E polycaprolactone polymer was used. In Table 2a the tone polymer P767E polycaprolactone polymer is designated PCL.
[93] The material used as the humectant was commercially available from Petrol Corporation, Tulsa, Oklahoma, under the trade name Unitox 480 Ethoxylated Alcohol, which has a number average molecular weight of about 2250 and an ethoxylation rate of about 80 weight. %, Melting point about 65 ° C., and HLB value about 16. In Table 2b the Unitox 480 ethoxylated alcohol is designated as wetting agent A.
[94] The material used as the humectant was commercially available from Baker Petrolite Corporation, Tulsa, Oklahoma under the trade name UNICID® X-8198 acid amide ethoxylate, which is HLB. The value is about 35 and the melting point is about 60 ° C. In Table 2b the unacidic X-8198 acid amide ethoxylate is designated as wetting agent B.
[95] The material used as the humectant was commercially available from Long-Fran, Cranbury, NJ, under the tradename IEPAL RC-630 ethoxylated alkyl phenol surfactant, which had an HLB value of about 12.7 and a melting point of about 4 ° C. . In Table 2b, IEPAL RC-630 ethoxylated alkyl phenol surfactants are designated as wetting agents C.
[96] Substance brand nameL: D ratioMelting Point (℃)Weight average molecular weightNumber average molecular weightPolydispersity indexResidual Lactic Acid Monomer Heflon A100005100: 0175187,000118,0001.58Less than 1% Tone P767EN / A6460,00043,0001.40N / A Bionole 1020N / A9540,000 to 1,000,00020,000 to 300,000About 2 to about 3.3N / A Bionole 3020N / A11440,000 to 1,000,00020,000 to 300,000About 2 to about 3.3N / A
[97] <Production of Sample>
[98] To prepare a particular thermoplastic composition, the various components were first dry mixed and melt blended in a counter-rotating twin-screw extruder to vigorously mix the components. The specific materials used in the examples below and the relative amounts of each material are listed in Tables 2a and 2b. The melt mixing includes melting the components partially or completely by the shearing effect of the rotary mixing screw. These conditions assist in the optimal blending and dispersion of the components of the thermoplastic composition. Haake Rheocord 90 pair-screw extruders available from Haake GmbH, Karlsauthe, Germany or Brabender Instruments, available from Brabender Instruments, South Hakken, NJ. Twin-screw extruders such as twin-screw mixers (product number 05-96-000), or other comparable twin-screw extruders, are suitable. This includes co-rotating twin-screw extruders, such as the ZSK-30 extruder available from Warner and Pfleiderer Corporation, Ramsay, NJ. Unless otherwise noted, all samples were prepared in a Hake Leocord 90 twin-screw extruder. The molten composition was cooled by extruding from a liquid cooled roll or melt mixer on the surface and / or by pushing air into the extrudate. The cooled composition was then pelletized to convert to fibers.
[99] The resin was converted to fibers and nonwovens on a self-fabricated spinning line with a 0.75 inch (1.905 cm) diameter extruder. The extruder had an L: D (length: diameter) ratio screw of 24: 1 and had three heating zones fed from the extruder to the transfer pipe leading to the spinning device. The transmission pipe includes the fourth and fifth heating zones and is a 0.62 inch diameter KOCH® trademark available from Koch Engineering Company Inc., New York, NY. It contained an SMX type static mixing device. The transfer pipe extends into the spinning head (sixth heating zone) and passes through a number of small hole spinnerets that extrude the molten polymer. The temperature of the heating zone for each composition is listed in Table 2b. The spin plate used herein had 15 holes and each hole had a diameter of 20 mils (0.508 mm). Air was quenched using air at 13-22 ° C., stretched using mechanical draw rolls, and passed through a wind drawer for harvesting or a fiber drawing apparatus for spunbond formation and bonding. Alternatively, other accessories for pre-collection treatment may be used. The contact angle was then measured for the undrawn free-fall fibers and the melt rheology for the pelletized resin. The results are shown in Table 3.
[100] <Examples 1 to 7>
[101] In this example, the same amount of Bionole 1020 polybutylene succinate and Bionole 3020 polybutylene succinate-co-adipate polymer were prepared on a ZSK-30 co-rotating twin-screw extruder manufactured by Warner & Player. The two components were mixed vigorously by melt blending with a. The strand thus obtained was pelletized by air cooling. The pellet thus obtained is dry mixed with adipic acid (product number AD 130 available from Spectrum Quality Products, Inc.) and Unitox 480 ethoxylated alcohol wetting agent, followed by the method described above. Melt blended and spun into fibers. Three of these examples (Samples 1, 3, and 4) were applied to the Lugi process and calendar to obtain a nonwoven web. Cup fracture and tensile tests were performed on this web and the results are shown in Table 4.
[102] <Example 8>
[103] In this example, the same amount of Bionole 1020 polybutylene succinate and Bionole 3020 polybutylene succinate-co-adipate polymer were prepared on a ZSK-30 co-rotating twin-screw extruder manufactured by Warner & Player. The two components were mixed vigorously by melt blending with a. The strand thus obtained was pelletized by air cooling. The pellet so obtained is dry mixed with malonic acid (product number M129-6, available from Aldrich Chemical Company, Milwaukee, WI) and a Unitox 480 ethoxylated alcohol wetting agent, according to the method described above. Melt blended and spun into fibers. Due to the severe expansion of the die and the dripping of polymers, attempts to make fibers have not been successful.
[104] Example 9
[105] In this example, the same amount of Bionole 1020 polybutylene succinate and Bionole 3020 polybutylene succinate-co-adipate polymer were prepared on a ZSK-30 co-rotating twin-screw extruder manufactured by Warner & Player. The two components were mixed vigorously by melt blending with a. The strand thus obtained was pelletized by air cooling. The pellets thus obtained are dry mixed with glutaric acid (product number G340-7 available from Aldrich Chemical Company, Milwaukee, WI) and Unitox 480 ethoxylated alcohol wetting agent, followed by the method described above. Melt blended and spun into fibers.
[106] <Example 10>
[107] In this example, the same amount of Bionole 1020 polybutylene succinate and Bionole 3020 polybutylene succinate-co-adipate polymer were prepared on a ZSK-30 co-rotating twin-screw extruder manufactured by Warner & Player. The two components were mixed vigorously by melt blending with a. The strand thus obtained was pelletized by air cooling. The pellet so obtained is dry mixed with Suberic acid (product number S520-0, available from Aldrich Chemical Company, Milwaukee, WI) and Unitox 480 ethoxylated alcohol wetting agent, followed by the method described above. Melt blended and spun into fibers.
[108] <Example 11>
[109] In this example, the same amount of Bionole 1020 polybutylene succinate and Bionole 3020 polybutylene succinate-co-adipate polymer were prepared on a ZSK-30 co-rotating twin-screw extruder manufactured by Warner & Player. The two components were mixed vigorously by melt blending with a. The strand thus obtained was pelletized by air cooling. The pellets thus obtained were dry mixed with adipic acid (product number AD130 available from Spectrum Quality Products, Inc.) and Izepal RC-630 ethoxylated alkyl phenol wetting agent, followed by melt blending and spinning into fibers according to the method described above. .
[110] <Example 12>
[111] In this example, the same amount of Bionole 1020 polybutylene succinate and Bionole 3020 polybutylene succinate-co-adipate polymer were prepared on a ZSK-30 co-rotating twin-screw extruder manufactured by Warner & Player. The two components were mixed vigorously by melt blending with a. The strand thus obtained was pelletized by air cooling. The pellets thus obtained are dry mixed with adipic acid (product number AD130 available from Spectrum Quality Products, Inc.) and unsided X-8198 acid amide ethoxylate wetting agent, followed by melt blending and fiber as described above. Spun.
[112] <Examples 13 to 20>
[113] In this example, the tone polymer P767E polycaprolactone polymer is melt blended with adipic acid (product number AD130 available from Spectrum Quality Products Inc.) and Unitox 480 ethoxylated alcohol wetting agent and fiber according to the method described above. Samples were prepared.
[114] Example 21
[115] In this example, the tone polymer P767E polycaprolactone polymer was melt blended with citric acid (product number 24,062-1, commercially available from Aldrich Chemical Company, Milwaukee, WI) and Unitox 480 ethoxylated alcohol wetting agent and the method described above. Spun into fibers accordingly. The melted resin bubbled and swelled, so no fiber sample was produced.
[116] <Examples 22 to 26>
[117] In this example, the Heplon A10005 poly (lactic acid) polymer is melt blended with adipic acid (product number AD130 available from Spectrum Quality Products Inc.) and Unitox 480 ethoxylated alcohol wetting agent and fiber according to the method described above. Samples were prepared. For Samples 23 and 24, due to the incompatibility of the polylactic acid, adipic acid, and Unitox 480 ethoxylated alcohol wetting agent, the extrudate strand was rocking and the wetting agent splashed, making the compounding very difficult.
[118] Those skilled in the art will recognize that the present invention can be changed and changed without departing from the scope of the present invention. Accordingly, the foregoing detailed description and examples are merely for illustrative purposes, and are not intended in any way to limit the scope of the invention as set forth in the appended claims.
[119] Sample numberPolymer (g)Polymer weight%Polycarboxylic acid (g)Polycarboxylic Acid Weight% PBSPBSAPCLHeflonAdipic acidCitric acidMalonic acidGlutaric acidSubersan 1 ^* 750750 100 0 2 ^* 637.5637.5 8522515 3675675 88.21509.8 4637.5637.5 83.322514.7 5637.5637.5 77.322513.6 6637.5637.5 74.022513.0 7562.5562.5 74.337524.7 8 ^* 637.5637.5 83.3 225 14.7 9637.5637.5 83.3 225 14.7 10637.5637.5 83.322514.7 11 ^* 637.5637.5 83.322514.7 12 ^* 637.5637.5 83.322514.7 13 ^* 1500 100 0 14 ^* 1125 75.037525.0 15 1125 74.337524.7 16 1125 71.437523.8 17 1125 65.237521.7 18 ^* 750 49.575049.5 19 ^* 1500 99.0 0 20 ^* 1500 87.0 0 21 ^* 1125 74.3 375 24.7 22 ^*1500100 0 23 ^*135090.015010.0 24 ^*112575.037525.0 25 ^*112574.337524.7 26 ^*112573.537524.5 * Not an embodiment of the invention
[120] Sample numberHumectant (g)Wetting Agent Weight%Extrusion temperature (℃)Fiber spinning temperature (℃) ABC 1 ^*0120/127/123/138180/180/185/190/190/195 2 ^*0122/127/132/130140/155/155/165/165/165 330 2.0122/127/132/130140/155/155/165/165/165 430 2.0122/127/132/130140/155/155/165/165/165 5150 9.1125/127/130/132140/145/145/150/150/150 6225 13.0125/127/130/132140/145/145/150/150/150 715 1.0125/127/130/132130/130/135/135/140/143 8 ^* 30 2.0125/130/132/135Not processed 930 2.0125/130/135/135135/140/140/145/150/150 1030 2.0125/130/135/135140/140/150/150/155/155 11 ^* 302.0125/127/130/132140/145/145/150/150/150 12 ^* 30 2.0125/127/130/132140/145/145/150/150/150 13 ^*0Not used190/190/195/195/200/205 14 ^*0135/137/145/147145/150/150/155/155/155 1515 1.0115/120/122/110140/140/145/145/145/150 1675 4.8120/126/126/118120/125/130/130/130/135 17225 13.160/70/70/80120/120/120/125/125/130 18 ^* 15 1.0120/125/125/122130/130/135/135/140/140 19 ^* 15 1.060/62/64/70160/160/160/165/170/175 20 ^* 225 13.060/62/64/70160/160/160/165/170/175 21 ^* 15 1.090/100/100/90Not processed 22 ^*0Not used160/180/190/190/190/190 23 ^*0155/155/165/165155/155/160/160/160/165 24 ^*0155/175/185/185150/170/165/160/160/160 25 ^* 15 1.0165/170/170/150150/150/155/160/160/165 26 ^* 30 2.0165/167/167/145150/150/155/160/160/165 * Not an embodiment of the invention
[121] Sample numberForward contact angleReverse contact angleContact angle hysteresisShear Viscosity at 1000 s ^-1 and 170 ° C (Pas) 1 ^* 977027203 2 ^* 83245956 358273161 453272650 560411918 652411111 768165224 8 ^* N / AN / AN / AN / A 962154713 1056193724 11 ^* 93385640 12 ^* 80552534 13 ^* 866125243 14 ^* 81542754 1562362645 1662352724 1749331611 18 ^* 7240329 19 ^* 49418257 20 ^* 544014179 21 ^* N / AN / AN / AN / A 22 ^* 875532N / A 23 ^* 75552023 24 ^* 85562912 25 ^* 79453424 26 ^* 76383815 * Not an embodiment of the invention
[122] Sample numberTensile propertiesCup shredding properties Load (g)Breaking load (g)Total energy (g · mm)Load (g) One168153666 341440219913 485683724817

权利要求:
Claims (38)
[1" claim-type="Currently amended] a. Polybutylene succinate polymer, polybutylene succinate-co-adipate polymer, polycaprolactone, having a weight average molecular weight of about 10,000 to about 2,000,000 and present in an amount of less than about 40 to 100% by weight in the thermoplastic composition Aliphatic polyester polymers selected from the group consisting of polymers, mixtures of these polymers, and copolymers of these polymers;
b. Multicarboxylic acids having less than about 30 carbon atoms in total and present in an amount from greater than 0 to about 30 weight percent in the thermoplastic composition; And
c. Wetting agents that have a hydrophilic-lipophilic balance ratio of about 10 to about 40 and are present in the thermoplastic composition in an amount greater than 0 to about 25 weight percent (all weight percents in the a, b, and c above are aliphatic polyester polymers present in the thermoplastic composition). Based on the total weight of the polycarboxylic acid and the humectant)
And a apparent viscosity value of about 5 to about 200 Pa.s at a temperature of about 170 ° C. and a shear rate of about 1000 s ⁻¹ .
[2" claim-type="Currently amended] The thermoplastic composition of claim 1 wherein the aliphatic polyester polymer is a polybutylene succinate polymer.
[3" claim-type="Currently amended] The thermoplastic composition of claim 1 wherein the aliphatic polyester polymer is a polybutylene succinate-co-adipate polymer.
[4" claim-type="Currently amended] The thermoplastic composition of claim 1 wherein the aliphatic polyester polymer is a polycaprolactone polymer.
[5" claim-type="Currently amended] The thermoplastic composition of claim 1, wherein the aliphatic polyester polymer is present in the thermoplastic composition in an amount of about 50 to about 95 weight percent.
[6" claim-type="Currently amended] 6. The thermoplastic composition of claim 5, wherein the aliphatic polyester polymer is present in the thermoplastic composition in an amount of about 60 to about 90 weight percent.
[7" claim-type="Currently amended] The thermoplastic composition of claim 1, wherein the multiple carboxylic acids are selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and mixtures of these acids.
[8" claim-type="Currently amended] 8. The thermoplastic composition of claim 7, wherein the multiple carboxylic acids are selected from the group consisting of glutaric acid, adipic acid and suberic acid.
[9" claim-type="Currently amended] The thermoplastic composition of claim 1, wherein the multiple carboxylic acids are present in the thermoplastic composition in an amount of about 1 to about 30 weight percent.
[10" claim-type="Currently amended] The thermoplastic composition of claim 9, wherein the multiple carboxylic acids are present in the thermoplastic composition in an amount of about 5 to about 25 weight percent.
[11" claim-type="Currently amended] The thermoplastic composition of claim 1, wherein the multiple carboxylic acids have a total of about 4 to about 30 carbon atoms.
[12" claim-type="Currently amended] The thermoplastic composition of claim 1, wherein the wetting agent exhibits a hydrophilic-lipophilic balance ratio of about 10 to about 20.
[13" claim-type="Currently amended] The thermoplastic composition of claim 1, wherein the humectant is present in the thermoplastic composition in an amount of about 0.5 to about 20 weight percent.
[14" claim-type="Currently amended] The thermoplastic composition of claim 1, wherein the humectant is present in the thermoplastic composition in an amount of about 1 to about 15 weight percent.
[15" claim-type="Currently amended] The thermoplastic composition of claim 1, wherein the wetting agent is selected from the group consisting of ethoxylated alcohols, acid amide ethoxylates, and ethoxylated alkyl phenols.
[16" claim-type="Currently amended] The method of claim 1, wherein the aliphatic polyester polymer is present in the thermoplastic composition in an amount of about 50 to about 95 weight percent; The polycarboxylic acid is selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and mixtures of these acids, in an amount of about 1 to about 30% by weight in the thermoplastic composition. Exists; And the humectant is selected from the group consisting of ethoxylated alcohols, acid amide ethoxylates, and ethoxylated alkyl phenols, the thermoplastic composition being present in the thermoplastic composition in an amount of about 0.5 to about 20 weight percent.
[17" claim-type="Currently amended] a. Polybutylene succinate polymer, polybutylene succinate-co-adipate polymer, polycaprolactone, having a weight average molecular weight of about 10,000 to about 2,000,000 and present in an amount of less than about 40 to 100% by weight in the thermoplastic composition Aliphatic polyester polymers selected from the group consisting of polymers, mixtures of these polymers, and copolymers of these polymers;
b. Multiple carboxylic acids having less than about 30 carbon atoms in total and present in an amount from greater than 0 to about 30 weight percent in the thermoplastic composition; And
c. Wetting agents that have a hydrophilic-lipophilic balance ratio of about 10 to about 40 and are present in the thermoplastic composition in an amount greater than 0 to about 25 weight percent (all weight percents in the a, b, and c above are aliphatic polyester polymers present in the thermoplastic composition). Based on the total weight of the polycarboxylic acid and the humectant)
And a mixture having a advancing contact angle value of less than about 70 degrees and a receding contact angle value of less than about 60 degrees.
[18" claim-type="Currently amended] 18. The fiber of claim 17, wherein the aliphatic polyester polymer is present in the thermoplastic composition in an amount of about 50 to about 95 weight percent.
[19" claim-type="Currently amended] 19. The fiber of claim 18 wherein the aliphatic polyester polymer is present in the thermoplastic composition in an amount of about 60 to about 90 weight percent.
[20" claim-type="Currently amended] 18. The fiber of claim 17 wherein the multiple carboxylic acids are selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and mixtures of these acids.
[21" claim-type="Currently amended] 21. The fiber of claim 20 wherein the multiple carboxylic acids are selected from the group consisting of glutaric acid, adipic acid and suberic acid.
[22" claim-type="Currently amended] 18. The fiber of claim 17, wherein the multiple carboxylic acids are present in the thermoplastic composition in an amount of about 1 to about 30 weight percent.
[23" claim-type="Currently amended] The fiber of claim 22, wherein the multiple carboxylic acids are present in the thermoplastic composition in an amount of about 5 to about 25 weight percent.
[24" claim-type="Currently amended] 18. The fiber of claim 17, wherein the multiple carboxylic acids have from about 4 to about 30 carbon atoms in total.
[25" claim-type="Currently amended] 18. The fiber of claim 17, wherein the wetting agent exhibits a hydrophilic-lipophilic balance ratio of about 10 to about 20.
[26" claim-type="Currently amended] 18. The fiber of claim 17 wherein the humectant is present in the thermoplastic composition in an amount of about 0.5 to about 20 weight percent.
[27" claim-type="Currently amended] 27. The fiber of claim 26 wherein the humectant is present in the thermoplastic composition in an amount of about 1 to about 15 weight percent.
[28" claim-type="Currently amended] 18. The fiber of claim 17 wherein the wetting agent is selected from the group consisting of ethoxylated alcohols, acid amide ethoxylates and ethoxylated alkyl phenols.
[29" claim-type="Currently amended] The fiber of claim 17 wherein the forward contact angle value is less than about 65 degrees.
[30" claim-type="Currently amended] 18. The fiber of claim 17 wherein the reverse contact angle value is less than about 55 degrees.
[31" claim-type="Currently amended] 18. The fiber of claim 17 wherein the reverse contact angle value is less than about 50 degrees.
[32" claim-type="Currently amended] 18. The method of claim 17, wherein the aliphatic polyester polymer is present in the thermoplastic composition in an amount of about 50 to about 95 weight percent; The polycarboxylic acid is selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and mixtures of these acids, in an amount of about 1 to about 30% by weight in the thermoplastic composition. Exists; And the wetting agent is selected from the group consisting of ethoxylated alcohols, acid amide ethoxylates and ethoxylated alkyl phenols, the fiber being present in the thermoplastic composition in an amount of about 0.5 to about 20% by weight.
[33" claim-type="Currently amended] 18. The fiber of claim 17 wherein the aliphatic polyester polymer is a polybutylene succinate polymer, the polycarboxylic acid is adipic acid and the wetting agent is an ethoxylated alcohol.
[34" claim-type="Currently amended] 18. The fiber of claim 17 wherein the aliphatic polyester polymer is a polybutylene succinate-co-adipate polymer, the polycarboxylic acid is adipic acid and the wetting agent is an ethoxylated alcohol.
[35" claim-type="Currently amended] 18. The fiber of claim 17 wherein the aliphatic polyester polymer is a mixture of polybutylene succinate polymer and polybutylene succinate-co-adipate polymer, the polycarboxylic acid is adipic acid, and the wetting agent is an ethoxylated alcohol.
[36" claim-type="Currently amended] 18. The fiber of claim 17 wherein the aliphatic polyester polymer is a mixture of polybutylene succinate polymer and polybutylene succinate-co-adipate polymer, the polycarboxylic acid is glutaric acid and the wetting agent is an ethoxylated alcohol.
[37" claim-type="Currently amended] 18. The fiber of claim 17 wherein the aliphatic polyester polymer is a mixture of polybutylene succinate polymer and polybutylene succinate-co-adipate polymer, the polycarboxylic acid is suberic acid, and the wetting agent is an ethoxylated alcohol.
[38" claim-type="Currently amended] 18. The fiber of claim 17 wherein the aliphatic polyester polymer is a polycaprolactone polymer, the polycarboxylic acid is adipic acid and the humectant is an ethoxylated alcohol.

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同族专利:

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公开号 | 公开日

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AU752865B2|2002-10-03|

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GT199900141A|2001-02-15|

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RU2001108497A|2004-03-20|

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WO2000012606A3|2000-06-02|

---

CO5100963A1|2001-11-27|

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KR100591649B1|2006-06-20|

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PE20001146A1|2000-10-25|

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BR9913274A|2001-10-09|

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WO2000012606A2|2000-03-09|

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UY25685A1|2000-03-31|

---

ZA200100865B|2001-07-16|

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JP2002523592A|2002-07-30|

---

MY132877A|2007-10-31|

---

US6225388B1|2001-05-01|

---

AU1633700A|2000-03-21|

---

EP1107999A2|2001-06-20|

---

AR021471A1|2002-07-24|

---

CN1318084A|2001-10-17|

---

PA8479501A1|2000-09-29|

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WO2000012606A9|2000-08-03|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1998-08-31|Priority to US09/144,153

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1998-08-31|Priority to US09/144,153

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1999-08-27|Application filed by 로날드 디. 맥크레이, 킴벌리-클라크 월드와이드, 인크.

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2001-07-31|Publication of KR20010073030A

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2006-06-20|Application granted

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2006-06-20|Publication of KR100591649B1

优先权:

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申请号 | 申请日 | 专利标题

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US09/144,153|1998-08-31|

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US09/144,153|US6225388B1|1998-08-31|1998-08-31|Biodegradable thermoplastic composition with improved wettability|