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WO2025250291A1 - Dispersion de polymère biodégradable et papier revêtu - Google Patents

Dispersion de polymère biodégradable et papier revêtu

Info

Publication number
WO2025250291A1
WO2025250291A1 PCT/US2025/027064 US2025027064W WO2025250291A1 WO 2025250291 A1 WO2025250291 A1 WO 2025250291A1 US 2025027064 W US2025027064 W US 2025027064W WO 2025250291 A1 WO2025250291 A1 WO 2025250291A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
biodegradable polymer
biodegradable
weight
aqueous dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/027064
Other languages
English (en)
Inventor
Erin B. Vogel
David L. Malotky
Derrick I. KO
Mary Alice UPSHUR
Yung Wei HSIAO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Rohm and Haas Co
Original Assignee
Dow Global Technologies LLC
Rohm and Haas Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC, Rohm and Haas Co filed Critical Dow Global Technologies LLC
Publication of WO2025250291A1 publication Critical patent/WO2025250291A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a composition comprising an aqueous dispersion of biodegradable polymer particles, a method of preparing the composition, and a method of preparing a coated substrate comprising the composition.
  • the composition is useful as a coating applied to a substrate, particularly a paper substrate.
  • the coated paper is useful as a single layered barrier coated paper or paperboard.
  • Coating of paper or paperboard for use in a range of applications, including packaging is known to provide barriers to a wide range of substances including oxygen, water, oil, and acids.
  • some are adopting paper packaging to replace traditional plastic packaging because of the higher recycling rates and mature recycling infrastructure for paper as compared to other types of recycled materials, such as plastics.
  • it should be coated with a polymeric material that does not interfere with the repulping and recycling process.
  • high- performance compostable barrier products that do not interfere with recyclability.
  • Aliphatic polyesters have been identified as attractive polymers for compostable materials because of their ability to biodegrade and provide barrier properties towards liquid water and oil/grease, while providing promising mechanical properties.
  • WO 2024/026140 Al discloses a biodegradable aqueous mixture for coating substrates, the mixture comprising: from 35 to 75 weight percent water and from 25 to 65 weight percent solids, wherein the solids comprise from 40 to 99 weight percent of a first poly(hydroxyalkanoate) based on the total dry weight of the solids, and wherein the first poly (hydroxy alkanoate) comprises at least 1 mole percent monomer repeat units of 3- hydroxypropionate.
  • WO 2024/026140 Al discloses a broad list of biodegradable polymers that can make up the solids portion including poly (vinyl alcohol), along with a broad list of potential surfactants, rheology modifiers, wetting agents, biocides, coalescing agents, and fillers to provide an aqueous mixture with a particle size of less than 20 microns.
  • WO 2024/026140 Al discloses that the mixture, when applied as a substrate coating, has an oxygen transmission rate of less than 50 cc/m 2 /24 h, as determined according to ASTM D3985.
  • WO 2024/026140 Al fails to provide any examples, lists only mixing as the process employed, discloses materials that would be detrimental to water barrier properties, and provides no guidance as to how to achieve any of the stated attributes for the aqueous mixture.
  • United States Patent 10,087,326 B2 discloses an aqueous-based dispersion of a hydrolytically unstable polymer which is substantially free of volatile organic compounds, consisting of biodegradable polymer particles, stabilizing agent, and optionally one or more components selected from viscosity increasing rheology modifiers and pH buffering agents in water, wherein the stabilizing agent consists of polyvinyl alcohol. Some of the materials disclosed, including use of poly vinyl alcohol, would be detrimental to water barrier properties.
  • the present invention provides a composition comprising a melt-blended, mechanically sheared aqueous dispersion of biodegradable polymer particles, wherein: (a) the biodegradable polymer in the aqueous dispersion comprises one or more aliphatic polyesters that meet the ASTM D5338/ISO14855 biodegradable standard and has a crystalline melting point of 60 to 120 °C; (b) the aqueous dispersion comprises one or more surfactants in the range of 1 to 20 percent by weight, based on the weight of the biodegradable polymer resin; (c) the composition is free of polyvinyl alcohol; and (d) the composition is biodegradable in accordance with ASTM D5338/ISO14855, has a concentration of polymer solids of at least 25 weight percent, a viscosity of less than or equal to 5000 centipoise (cP), and a mean volume (Vmean) particle size in the range of 100 nanometers (nm) to 10
  • the present invention further provides a method of preparing a composition comprising an aqueous dispersion of biodegradable polymer particles, comprising blending biodegradable polymer, water, and surfactant(s) together via a mechanical shear mixing device at temperatures above the melting temperature of the highest melting component in the dispersion formulation for up to 90 minutes, wherein: (a) the biodegradable polymer in the aqueous dispersion comprises one or more aliphatic polyesters that meet the ASTM D5338/ISO14855 biodegradable standard and has a crystalline melting point of 60 to 120 °C; (b) the aqueous dispersion comprises one or more surfactants in the range of 1 to 20 percent by weight, based on the weight of the biodegradable polymer resin; (c) the composition is free of polyvinyl alcohol; and (d) the composition is biodegradable in accordance with ASTM D5338/ISO14855, has a concentration of polymer solids of at least 25 weight percent, a vis
  • composition comprising an aqueous dispersion of biodegradable polymer particles may be prepared by a continuous or batch process that employs melt-blending and mechanical shear mixing.
  • a continuous process is preferred because of the lower residence time at elevated temperatures.
  • dispersing devices like overhead mixers are suitable for dispersion temperatures below 100°C, while an enclosed reactor is used for processes requiring temperatures above 100°C.
  • High-shear agitators such as cowles blades, are used at speeds between 600 and 1800 rpm and durations of 10 to 90 minutes to generate the dispersion.
  • the materials base resin/polymer, surfactant, modifiers, and water) are combined.
  • Dilution water can be added during this mixing period or as a post-add to achieve the desired solids level.
  • the batch process can be carried out, for example, using a pressurized helical batch mixer such as a 2CV Helicone mixer, which is a conical batch mixer that uses dual intermeshing conical blades to mix high viscosity materials.
  • the polymer and dispersant are fed into a twin-screw extruder using a controlled rate feeder at a set feed rate.
  • the solid polymer is delivered by a gravimetric feeder, and the liquid dispersant is delivered by an IscoTM syringe pump (Teledyne Instruments, Inc.) into the melt zone of the extruder.
  • the polymer and dispersant are forwarded through the extruder and combined to form a liquid melt material where the melt zone temperature in the extruder is set to 15°C higher than the melting temperature of the highest melting component in the dispersion formulation.
  • An initial amount of water and base and optionally stabilizer is then added into the extruder.
  • dilution water and optionally stabilizer is then added.
  • the total amount of dilution water can be split into one or more locations along the length of the extruder. If the optional stabilizer is added with the dilution, it is ideally added in the first dilution location.
  • the extruder speed used can be 600 rpm.
  • a backpressure regulator may be used to adjust the pressure inside the extruder barrel to a pressure adapted to reduce steam formation (generally the pressure is from 2 MPa to 4 MPa).
  • Each polymer dispersion exits from the extruder and is filtered first through a 200 micrometer (pm) filter.
  • An example of a preferred continuous process is twin screw extrusion, as described in U.S. Patent 8,722,787, Comparative Example E.
  • An example of a preferred twin screw extruder is described in U.S. Patent 9,278,473.
  • the biodegradable polymer in the aqueous dispersion comprises one or more aliphatic polyesters that meet the ASTM D5338/ISO14855 biodegradable standard and has a crystalline melting point of 60 to 120 °C.
  • aliphatic polyesters include polylactide (PLA), polycaprolactone (PCL), polyhydroxyalkanoates (PHAs), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), or combinations thereof; however, few of these materials are available as aqueous dispersions.
  • PHA polylactide
  • PCL polycaprolactone
  • PHAs polyhydroxyalkanoates
  • PBS polybutylene succinate
  • PBSA polybutylene succinate adipate
  • These aliphatic polyesters can be produced via fermentation or chemical transformation including catalysis.
  • the ideal polyester will have a crystalline melting point below that of traditional paper drying ovens, or less than 100 °C ( ⁇ 100 °C).
  • the aliphatic polyesters of the present invention are preferably one or more of PBS, PBS A, PCL and P3HP materials, where P3HP means poly(3-hydroxypropionate) and where PBS(A) means PBS and/or PBSA.
  • PBS(A) and P3HP have good barrier properties to liquid water and oil/grease, they are heat sealable, and they biodegrade under industrial composting conditions.
  • These polymers also have low glass transition temperatures and lower melting points compared to other aliphatic polyesters, enabling flexible coatings that can be formed at the same cure temperatures used for existing non- biodegradable barrier dispersions.
  • the lower melting point also improves the processability of these polymers as their melting point is much below their degradation temperature.
  • the biodegradable polymer in the aqueous dispersion contains less than five percent ( ⁇ 5%), preferably less than two percent ( ⁇ 2%), more preferably less than one percent ( ⁇ 1%), and most preferably zero percent (0%) of any water-soluble polymer, including polyvinyl alcohol, based on the weight of the biodegradable polymers in the composition. Zero percent is also referred to as being free of, or in the absence of, the water-soluble polymer.
  • composition of the present invention is biodegradable in accordance with ASTM D5338/ISO14855, whereby a sample that meets biodegradable standards will have at least ninety percent (90%) conversion of carbon in the sample to carbon dioxide (CO2).
  • ASTM D5338 biodegradation test method is an aerobic biodegradation test that introduces material to a mixed bacterial and fungal environmental inoculum and uses respirometry to measure biodegradation.
  • Standard testing for ASTM D5338 is a minimum of 90 days in an aerobic and controlled composting environment.
  • ISO 14855 is a standard biodegradation test method that measures ultimate aerobic biodegradation by the analysis of evolved carbon dioxide. ISO 14855 includes standard testing for a minimum of 90 days and then the biodegradation results are determined after an analysis of evolved CO2.
  • the concentration of polymer solids in the composition is within the range of 25 to 75 weight percent (25-75 wt %), preferably 30 to 60 weight percent (30-60 wt %), based on the weight of water and the polymers combined. All individual values and subranges from 25 to 75 weight percent are included herein and disclosed herein.
  • the solids content of the coating composition is measured using an infrared solids analyzer such as an OHAUS® MB45 Moisture Analyzer (OHAUS Corporation, Parsippany, NJ, USA) or similar device.
  • the composition has a viscosity of preferably less than or equal to 5000 centipoise (cP), more preferably less than or equal to 2500 cP, most preferably less than or equal to 1000 cP, and preferably greater than or equal to 200 cP. All individual values and subranges from 200 to 5000 cP are included herein and disclosed herein.
  • the viscosity of the composition is measured using an RV viscometer at 50 rpm using the appropriate spindle for the given viscosity, such as an RV3 at 50 rpm.
  • a centipoise is one millipascal-second (mPa*s) in SI units.
  • the composition has a mean volume (Vmean) particle size preferably in the range of 100 nanometers (nm) to 10 microns ( m), more preferably in the range of 100 nm to 5 microns, and most preferably in the range of 100 nm to 2 microns. All individual values and subranges from 100 nm to 10 microns are included herein and disclosed herein.
  • the particle size of the solids particles of the coating composition is measured using a COULTERTM LS 13 -320 or LS 13 320 XR particle size analyzer (Beckman Coulter Corporation, Fullerton, CA).
  • high performance coatings such as those used for paper drink cups
  • high performance coatings are prepared by extrusion coating or lamination of a film directly onto the paper substrate, often with multiple film layers.
  • This layered approach can impart preferential properties to the paper substrate but can also increase processing time, add coating weight, and can negatively impact the recyclability of the paper substrate.
  • Compositions of the present invention provide an avenue to coat on paper as a waterborne coating at significantly lower coat weights than those achievable via traditional extrusion-based methods, allowing for repulping of the paper substrate it is applied to.
  • the coating composition can be applied to paper or paperboard using traditional wet applications known to those skilled in the art, such as a wire wound drawdown bar.
  • the wet film can then be allowed to dry or heated to remove water, and if heated, preferably to a temperature in the range of from 50 °C, more preferably from 70 °C to preferably 150 °C, more preferably 120 °C to provide a coat weight of from 1, preferably from 2, more preferably from 4, and most preferably from 6 g/m 2 , to 20, preferably to 15, more preferably to 10, and most preferably to 7 g/m 2 . All individual values and subranges from 1 to 20 g/m 2 are included herein and disclosed herein.
  • the paper or paperboard may be uncoated or pre-coated.
  • the aqueous dispersion of biodegradable polymer particles is dispersed and stabilized by a single surfactant or a blend of surfactants in a continuous aqueous phase.
  • concentration of surfactant(s) is between one to twenty percent (1 - 20 %), and preferably less than ten percent ( ⁇ 10%), by weight based on the biodegradable polymer resin. All individual values and subranges from 1 to 20% are included herein and disclosed herein.
  • the surfactants include nonionic, anionic, cationic, or combinations of nonionic and anionic, nonionic and nonionic, or nonionic and cationic.
  • anionic surfactants suitable for polyester emulsification include fatty carboxylic acid salts, sulfuric salt capped alkoxylate amine, and salts of acid functional alkyds resins.
  • suitable cationic surfactants include quaternary ammonium salt.
  • nonionic surfactants suitable for polyester emulsification include styrenated phenol alkoxylates, ethoxylate amine, linear and branched polyoxyethylene alcohol, alkyl modified polyoxyethylene/polyoxypropylene copolymer (such as butyl) (available under the Tergitol brand name, X series), and polyethylene glycol phenyl ether (such as PEG octyl phenol ether).
  • Surfactants in the category of polyoxyethylene(EO)-polyoxypropylene(PO) block copolymers include poloxamers, such as poloxamer 238, 338, 407, 184, and 331 or Pluronic F88, F108, F127, P-105, L64, and L101. Surfactants in these categories require a sufficient EO chain length, typically greater than ten (> 10). Alkyl and fatty alcohol polyglucoside (such as coco-, lauryl-, and decyl- glucoside) are preferred for the present invention aqueous dispersion and are available under the TritonTM CG and the EcoSenseTM series of products available from Dow, Inc. (Midland, MI, USA).
  • a blend of surfactants may improve dispersion particle size at high temperature, and long-term shelf stability at low temperature. It is also preferable to avoid saturated linear alkyl chains (such as lauryl, cetyl, and stearyl) as the hydrophobe despite structural similarities with some surfactant examples listed above, due to their lower compatibility with aliphatic polyesters.
  • Preferred hydrophobe chemistry includes polypropylene oxide moieties, or other oxygen continuing structures such as an alkyd or polyester similar in chemistry to the base polymer resin to be dispersed.
  • surfactants which are detrimental to the properties required for a coated paper substrate should be avoided.
  • examples of surfactants unsuitable for the aqueous dispersion of the present invention because of their detrimental effect on water barrier and brittleness of the coated material include nonionic polyvinyl alcohol or other water-soluble polymers and anionic strong acid salts, such as sodium lauryl sulfate. While it is best to avoid water-soluble surfactants, such as sodium lauryl sulfate and sodium laureth sulfate, such materials can be used at low levels of less than one percent ( ⁇ 1%), by weight based on the biodegradable polymer resin, to provide colloidal stability but not enough to act as a dispersant.
  • Additional stabilizing agents such as plasticizer and rheology modifiers may be added for the aqueous dispersion in some embodiments.
  • plasticizer and rheology modifiers may be added for the aqueous dispersion in some embodiments.
  • biopolymer polysaccharides and baseneutralized acrylic acid copolymer may be included in the dispersion.
  • concentrations of these modifiers are typically in a small quantity of less than ten percent ( ⁇ 10%) by weight based on the biodegradable polymer resin.
  • the aqueous dispersion may include additives such as non-degradable waxes (PE-based, diglycerides and triglycerides, other) at levels ranging from zero to ten weight percent (0-10 wt%) or biodegradable/semi-biodegradable waxes (plant-based such as carnauba, stearates) ranging from zero to thirty weight percent (0-30 wt%), by weight based on the biodegradable polymer resin.
  • additives such as non-degradable waxes (PE-based, diglycerides and triglycerides, other) at levels ranging from zero to ten weight percent (0-10 wt%) or biodegradable/semi-biodegradable waxes (plant-based such as carnauba, stearates) ranging from zero to thirty weight percent (0-30 wt%), by weight based on the biodegradable polymer resin.
  • Fatty acid amides in the range of 0-10 wt% and inorganic materials such as talc, kaolin clay, and/or calcium carbonate in the range of 0-75 wt%, by weight based on the biodegradable polymer resin, may also be included in the aqueous dispersion of the present invention.
  • inorganic materials such as talc, kaolin clay, and/or calcium carbonate in the range of 0-75 wt%, by weight based on the biodegradable polymer resin, may also be included in the aqueous dispersion of the present invention.
  • These additives have been shown to provide improvements to barrier performance properties (water, oil/grease) and block for paper coatings.
  • the aqueous dispersion of biodegradable polymer particles When the aqueous dispersion of biodegradable polymer particles is coated onto a paper substrate and subjected to a temperature of less than or equal to 130 degrees Celsius ( ⁇ 130 °C), but above the melting temperature of the biodegradable base resin, the dispersion particles coalesce to form a continuous coating of the biodegradable polymer.
  • the surfactant and other minor components in the dispersion can be entrained or encased into this coating in small domains that do not adversely affect the barrier of the coating.
  • the coating composition may optionally be mixed or formulated with one or more additional components as those skilled in the art can appreciate, such as for example, other waterbased dispersions, pigments, wetting agents, defoamers, solvents, rheology modifiers, surfactants, anti-oxidants, and other processing aids to improve barrier and performance attributes of the coated paperboard.
  • additional components such as for example, other waterbased dispersions, pigments, wetting agents, defoamers, solvents, rheology modifiers, surfactants, anti-oxidants, and other processing aids to improve barrier and performance attributes of the coated paperboard.
  • Such improvements include for example, compatibility with a substrate, dispersion wet out, coating flexibility, coating integrity upon exposure to extremes in temperature or radiation, flowability, heat seal, block resistance, and other attributes, as well as to lower cost in use.
  • Coated paper samples were prepared by applying dispersion compositions to a side of glassine paper weighing 62 grams per square meter (g/m 2 or gsm) using a motorized wire-wound rods drawdown machine (available from RK Printcoat Instruments). Speed and wire rod diameter were selected for each dispersion such that the final coat weight after curing was in the range of 8 to 10 gsm.
  • Coated paper was immediately cured in a ventilated forced air oven at specified cure temperature (100-120 °C) for 2 minutes. Coatings were left to acclimatize in a controlled temperature room (CTR) at 23 °C/50% relative humidity (RH) for at least two hours prior to testing barrier performance.
  • CTR controlled temperature room
  • RH relative humidity
  • the coat weight of samples was measured by cutting out 7.17 in 2 (46.26 cm 2 ) sections coated and uncoated paper, then placing the sections in an oven at 100 °C for 2 min. All the samples were then weighed, and the coat weight was determined by the difference between the coated and uncoated samples. Coat weight is represented as grams per square meter (gsm or g/m 2 ). Water Barrier Cobb Test
  • Water barrier is assessed following TAPPI T441, where a 2-inch by 2-inch piece of coated paper is pre-weighed then mounted in a 10 cm 2 Cobb Tester. 10 mL of water is then poured into the enclosed Cobb tester ring directly onto the coated paper surface. Water exposure time is for 30 minutes. After allotted time, the water is discarded, and the paper sample is removed. Excess water on the paper is removed by placing blotter paper on top of the sample and moving a hand roller once back and force over the pad without additional pressure. After surface is blotted dry, exposed test sample is re-weighed and weight of water uptake (Cobb value reported in grams per square meter) is determined by subtracting final weight vs.
  • TAPPI T441 where a 2-inch by 2-inch piece of coated paper is pre-weighed then mounted in a 10 cm 2 Cobb Tester. 10 mL of water is then poured into the enclosed Cobb tester ring directly onto the coated paper surface. Water exposure time is for 30 minutes. After allotted time, the water is discarded
  • Kit solutions typically range from 1 through 12 and contain a combination of castor oil, toluene, and n-heptane. Additional test solutions numbered 13-16 beyond the outlines of TAPPI T559 have been added to differentiate high performance coatings. While Kit solutions are adequate for evaluating fluorinated materials, these solutions can have unexpected interactions with other coating materials that complicate overall results. However, the KIT test is still widely used in the industry and remains a common evaluation for coatings.
  • one drop of intermediate KIT solution (7 or 8) is applied to the surface of the coated paper article for 15 seconds after which the drop is removed with a lab tissue. If test area appears darker in color or shows small dark spots after applying KIT solution, it indicates solution broke through barrier coating and test needs to be repeated on a new section of coated article with a lower numbered KIT solution.
  • the Kit solution number where no further breakthrough is observed is assigned to the coating, that is the highest Kit solution that does not cause discoloration on the paper surface is the Kit score value.
  • a Kit score greater than 6 and ideally greater than 8 indicate good oil and grease barrier for the coating.
  • folded Kit a second test referred to as folded Kit was also performed to test coating flexibility.
  • This test follows the same procedures described above and uses identical KIT solutions, but instead of testing on flat paper, folded kit test samples are creased prior to KIT solution exposure. Creasing is accomplished by hand (not a roller) in a “hamburger” orientation (crease runs horizontally across the coated paper) and KIT solutions are placed inside the valley of the crease.
  • Oil/grease resistance is also assessed using an oil breakthrough test.
  • the Ralston Purina 2 test is another test that evaluates a barrier’s ability to resist oil at elevated temperatures for a longer period of time.
  • coated substrates are cut into 2x2 inch squares and placed (coated side up) on top of a 2x2 inch square of printer paper to absorb any oil that might penetrate the experimental coated paper.
  • a cotton pad is placed on top of the experimental substrate and 0.6 mL of oil is pipetted onto the cotton pad carefully so that it absorbs and holds the oil.
  • a brass 55 g weight is then placed on top of the wet cotton pad.
  • the setup is placed into an environmental chamber, set at 60 °C and 50% RH, for 24 hours. Following the exposure, the printer paper is evaluated for oil penetration.
  • Paint VisionTM software (Dow, Inc.) is used for determination of the degree of oil penetration.
  • the oily pieces of printer paper are placed into a photo booth and images are captured.
  • the images are analyzed using a software program designed to identify the dark spots of oil on the absorbent printer paper and calculate the surface area percentage of the penetration and staining.
  • the test is done in 9 replicates and an average surface area of staining is the score. The lower the percentage of breakthrough the better the barriers’ resistance to hot oil. Ideal percentages are typically less than 25% breakthrough.
  • DSC can be used for polymer characterization.
  • Samples are prepared for DSC analysis by placing 5-10 mg of polymer in a hermetic pan. The pan is placed in an Agilent Q2000TM DSC instrument. The sample is heated from room temperature up to 125 °C and cooled down to -40 °C at a rate of 10 °C/min and finally heated back up to 125 °C at 10 °C/minute. The melting point is determined using Agilent Universal analysis software. Particle size measurement, viscosity, pH and solids measurements can be added as needed.
  • BioPBSTM FD72 is a bio-based polybutylene succinate adipate (PBSA) polymer available from Mitsubishi Chemical Performance Polymers.
  • CapaTM 6500 is a 50,000 g/mol molecular weight linear thermoplastic polycaprolactone diol polymer available from Ingevity.
  • PluronicTM Fl 08 is a 14,600 g/mol molecular weight poly(ethylene glycol)-poly(propylene glycol) triblock copolymer available from Merk and Sigma-Aldrich.
  • PovalTM 22-88 is a polyvinyl alcohol polymer available from Kuraray. Oleic acid is a fatty acid that occurs naturally in various animal and vegetable fats and oils.
  • Sodium laureth sulfate (or sodium lauryl ether sulfate) is an anionic surfactant.
  • Inventive and comparative dispersion compositions A to E were made in a continuous melt emulsification process using the raw materials and feed rates shown in Table 1 and the general process procedure and process conditions described below.
  • Table 1A shows the dispersion composition on a solids basis.
  • the thermoplastic polyester resin and dispersant listed for each example in Table 1 are fed into a 25 mm diameter twin screw extruder using a controlled rate feeder at the given feed rates listed in Table 1.
  • the solid polyester base resin was delivered by a gravimetric feeder, and the liquid dispersant was delivered by an Isco syringe pump into the melt zone of the extruder.
  • the polyester base resin and dispersant are forwarded through the extruder and combined to form a liquid melt material where the melt zone temperature in the extruder is set to 15 °C higher than the melting temperature of the highest melting component in the dispersion formulation.
  • An initial amount of water and base and optionally stabilizer is then added into the extruder.
  • additional dilution water and optionally stabilizer is then added.
  • the total amount of dilution water can be split into one or more locations along the length of the extruder. If the optional stabilizer is added with the dilution, it is ideally added in the first dilution location.
  • the extruder speed used was 600 rpm.
  • a backpressure regulator is used to adjust the pressure inside the extruder barrel to a pressure adapted to reduce steam formation (generally the pressure was from 2 MPa to 4 MPa).
  • Each polyester dispersion exits from the extruder and is filtered first through a 200 micrometer (pm) filter.
  • the resultant aqueous dispersion composition from the two processes has a solids content measured in weight percent (wt %); and the solids particles have a volume mean particle size measured in microns.
  • the solids content, average particle size (PS) of the solids particles, and viscosity of the aqueous dispersion composition from the continuous process are indicated in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)

Abstract

La présente invention concerne une composition comprenant une dispersion aqueuse de particules polymères biodégradables, un procédé de préparation de la composition, et un procédé de préparation d'un substrat revêtu comprenant la composition. La composition est utile en tant que revêtement appliqué sur un substrat, en particulier un substrat en papier. Le papier revêtu est utile en tant que papier ou carton à revêtement barrière monocouche.
PCT/US2025/027064 2024-05-28 2025-04-30 Dispersion de polymère biodégradable et papier revêtu Pending WO2025250291A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202463652405P 2024-05-28 2024-05-28
US63/652,405 2024-05-28

Publications (1)

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WO2025250291A1 true WO2025250291A1 (fr) 2025-12-04

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US8722787B2 (en) 2003-08-25 2014-05-13 Dow Global Technologies Llc Coating composition and articles made therefrom
US9278473B2 (en) 2009-12-04 2016-03-08 Union Carbide Chemicals & Plastics Technology Llc Extruder screw
US10087326B2 (en) 2016-02-29 2018-10-02 Michelman, Inc. Aqueous-based hydrolytically stable dispersion of a biodegradable polymer
WO2022113011A1 (fr) * 2020-11-26 2022-06-02 Consiglio Nazionale Delle Ricerche Dispersions aqueuses sans halogène de polymères biodégradables et procédé de préparation de ces dernières
WO2024026140A1 (fr) 2022-07-29 2024-02-01 Danimer Ipco, Llc Mélanges aqueux de nouveaux poly(hydroxyalcanoates)

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8722787B2 (en) 2003-08-25 2014-05-13 Dow Global Technologies Llc Coating composition and articles made therefrom
US9278473B2 (en) 2009-12-04 2016-03-08 Union Carbide Chemicals & Plastics Technology Llc Extruder screw
US20110237744A1 (en) * 2010-03-24 2011-09-29 Basf Se Process for producing aqueous dispersions of thermoplastic polyesters
US10087326B2 (en) 2016-02-29 2018-10-02 Michelman, Inc. Aqueous-based hydrolytically stable dispersion of a biodegradable polymer
WO2022113011A1 (fr) * 2020-11-26 2022-06-02 Consiglio Nazionale Delle Ricerche Dispersions aqueuses sans halogène de polymères biodégradables et procédé de préparation de ces dernières
WO2024026140A1 (fr) 2022-07-29 2024-02-01 Danimer Ipco, Llc Mélanges aqueux de nouveaux poly(hydroxyalcanoates)

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