WO2023240016A1 - Method for preparing a polyolefin coating for a paper substrate - Google Patents
Method for preparing a polyolefin coating for a paper substrate Download PDFInfo
- Publication number
- WO2023240016A1 WO2023240016A1 PCT/US2023/067808 US2023067808W WO2023240016A1 WO 2023240016 A1 WO2023240016 A1 WO 2023240016A1 US 2023067808 W US2023067808 W US 2023067808W WO 2023240016 A1 WO2023240016 A1 WO 2023240016A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fatty amide
- range
- primary fatty
- particles
- alkyl primary
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000000576 coating method Methods 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 title claims abstract description 13
- 229920000098 polyolefin Polymers 0.000 title claims description 17
- 239000000758 substrate Substances 0.000 title description 10
- 150000002193 fatty amides Chemical class 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 10
- -1 polypropylene Polymers 0.000 claims description 10
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 230000007704 transition Effects 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 19
- 230000005540 biological transmission Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920003298 Nucrel® Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000289 melt material Substances 0.000 description 1
- VMRGZRVLZQSNHC-ZCXUNETKSA-N n-[(z)-octadec-9-enyl]hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC VMRGZRVLZQSNHC-ZCXUNETKSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N n-hexene Natural products CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
Definitions
- the present invention relates to a method for preparing a thin polyolefin coating for a paper substrate.
- the coated paper has been found to have useful moisture vapor transmission rate properties.
- ultra-thin coatings can be prepared by applying a waterborne polyolefin emulsion onto the paper substrate, followed by curing; nevertheless, meeting targets for moisture vapor transmission rate (MVTR) and coefficient of friction (CoF) remain elusive. Accordingly, it would be an advance in the field of coated paper substrates to prepare a thin coating that meets the application requirements for MVTR and provides a recyclable package.
- MVTR moisture vapor transmission rate
- CoF coefficient of friction
- the present invention addresses a need in the art by providing a method comprising the steps of a) applying onto paper a composition comprising an aqueous dispersion of poly-Ca-Cs-olefin particles, a dispersant, and a Cs-Cze-alkyl primary fatty amide; and b) drying the composition to form a coating having a coat weight in the range of from 1 g/m 2 to 20 g/m 2 .
- the method of the present invention can be used to provide ultra-thin coatings on a paper substrate with advantageous moisture vapor transmission rate and coefficient of friction properties.
- the present invention is a method comprising the steps of a) applying onto paper a composition comprising an aqueous dispersion of poly-C2-C3-olefin particles, a dispersant, and a Cs-C26-alkyl primary fatty amide; and b) drying the composition to form a coating having a coat weight in the range of from 1 g/m 2 to 20 g/m 2 .
- poly-C2-C3-olefin particles refer to polyethylene particles, polypropylene particles, and poly(ethylene-propylene) copolymers particles.
- the polyethylene may be an ethylene-C4-Cio-a-olefin copolymer (i.e., linear low-density polyethylene) such as an ethylene- 1 -butene copolymer, an ethylene- 1— hexene copolymer, and an ethylene- 1 -octene copolymer.
- linear low-density polyethylene is AFFINITY PL1280 LLDPE Ethylene-Octene Copolymer (A Trademark of The Dow Chemical Company or its affiliates).
- the polyethylene may also be a high-density polyethylene, commercially available, for example, as DOWTM DMDA-8940 NT 7 HDPE Resin; or a low-density polyethylene.
- a commercially available ethylene-propylene copolymer is VERSIFYTM 4200 Propylene-Ethylene Copolymer (Trademarks of The Dow Chemical Company or its affiliates), and a commercially available polypropylene is Braskem 6D43 Random Copolymer.
- the particles which are believed to contain the C2-C3-polyolefin and some amount of the dispersant and the primary fatty amide associated therewith, preferably have a volume mean particle size in the range of from 200 nm or from 300 nm to 5 pm or to 3 pm or to 1.5 pm, as measured by dynamic light scattering.
- the dispersant is a copolymer of ethylene and a carboxylic acid monomer or a salt thereof.
- suitable dispersants include ethylene- acrylic acid copolymers, ethylene-methacrylic acid copolymers, and ethylene-itaconic acid copolymers, and lithium, sodium, and potassium salts thereof.
- the weight-to-weight ratio of structural units of ethylene to carboxylic acid monomer or salt thereof is preferably in the range of from 95:5, more preferably from 90: 10, and most preferably from 85:15; to 70:30, more preferably to 75:25.
- structural unit of the named monomer refers to the remnant of the monomer after polymerization.
- a structural unit of methacrylic acid is as illustrated: structural unit of methacrylic acid where the dotted lines represent the points of attachment of the structural unit to the polymer backbone.
- Examples of commercially available dispersants include PRIMACORTM 5980i Ethylene- Acrylic Acid Copolymer and NUCREL 960TM Ethylene- Methacrylic Acid Copolymer (Trademarks of The Dow Chemical Company or its affiliates).
- the C.5-C26-alkyl primary fatty amide may be linear or branched and may be saturated or partially unsaturated with one or two or three double bonds.
- the fatty amide may also be a Cio--C24-alkyl primary fatty amide or a Ci6-C22-alkyl primary fatty amide.
- suitable fatty amides include linear and branched Cis -alkyl mono-unsaturated fatty amides; linear and branched Cis-alkyl saturated fatty amides; linear and branched C22-alkyl mono-unsaturated fatty amides; and linear and branched C22-alkyl saturated fatty amides.
- the Cs-C26-alkyl primary fatty amide preferably has a melting point in the range of from 50 °C or from 65 °C to 115 °C or to 100 °C or to 90 °C.
- the concentration of the poly-C2-C3-olefin particles less any associated dispersant or primary fatty amide is preferably in the range of from 40 or from 60 or from 70 weight percent, to 95 or to 90 weight percent, based on the weight of the polyolefin, the dispersant, and the Cs-C26-alkyl primary fatty amide.
- the concentration of the dispersant is preferably in the range of from 4 or from 9, or from 15 weight percent, to 50, or to 40, or to 30 weight percent, based on the weight of the polyolefin particles, the dispersant, and the C5-C26 -alkyl fatty amide.
- the concentration of the Cs-C26-alkyl primary fatty amide is preferably in the range of from 0.5 or from 1 to 5 or to 4 or to 3 weight percent, based on the weight of the polyolefin particles, the dispersant, and the C5-C26-alkyl fatty amide.
- the pH of the composition is preferably in the range of from 8 to 11.
- a neutralizing agent such as KOH is advantageously used to adjust the pH to the desired level.
- the composition advantageously further comprises a stabilizing amount of an anionic surfactant such as a C10-C24 linear or branched alkyl or aralkyl carboxylate, sulfate, or phosphate; or a nonionic surfactant such as a secondary alcohol ethoxylate or an ethylene oxide propylene oxide block copolymer surfactant.
- an anionic surfactant such as a C10-C24 linear or branched alkyl or aralkyl carboxylate, sulfate, or phosphate
- a nonionic surfactant such as a secondary alcohol ethoxylate or an ethylene oxide propylene oxide block copolymer surfactant.
- coat weights in the range of 1 g/m 2 or from 2 g/m 2 or from 5 g/m 2 to 20 g/m 2 or to 12 g/m 2 or to 10 g/m 2 can be achieved with desirable moisture vapor transmission rate (MVTR) and coefficient of friction (CoF) properties.
- MVTR moisture vapor transmission rate
- CoF coefficient of friction
- UPM Brilliant 62 Glassine Paper (basis wt. 62 g/m 2 ) was coated with the polyolefin dispersion using a drawdown bar and dried in a forced air oven for 2 min at 100° C to a final coating areal density (coat weight) of 8 g/m 2 ( ⁇ 8 to 9 pm coating thickness). Coat weights were measured by punching holes in coated and uncoated UPM paper with a circular die to form discs having a specified diameter (D cm). The coated discs (Wl) were weighed against the uncoated disc (W2) and the coat weights were calculated by the formula:
- Moisture Vapor Transmission Rates were determined in accordance with
- ASTM E96/E96M A coated paper sample was sealed to the open end of a permeability cup followed by exposure of the sample to a controlled temperature and humidity environment (typically, a humidity chamber). MVTR was determined based by measuring mass uptake for the cup as a function of time.
- the dynamic coefficients of friction were measured using a Texture Analyzer with a sliding friction rig in accordance with TAPPI T549.
- a piece of coated paper was affixed to the bottom of a sled weighing 200 g with the coated side facing down.
- Another piece of coated paper was affixed to a plane with coated side facing up.
- a string was attached to the sled and pulled so that the sled traversed the plane at the speed of 2.5 mm/s for at least 100 mm.
- the plateaued force Fd (unit: gram force) for the constant moving of the sled was recorded.
- the degree of neutralization of the polyolefin dispersions was determined by the following equation:
- DoN 100 where W is the weight of the base added in g, EB is the equivalent weight of the base, Ai is the acid number of the ith component in units of mg KOH/g and the CD i is the weight fraction of the ith component in POD dispersion solid.
- Table 1 illustrates the components and feed rates used to prepare Examples 1-4 and Comparative Examples 1 -5. Feed rates are shown parenthetically. The general procedure is shown following Table 1.
- PO refers to the polyolefin
- Amide refers to the fatty amide
- ITO. refers to the initial water rate
- ILOd refers to the dilution water rate
- Solids refers to the wt.% solids of the polyolefin the dispersant, the fatty amide, and the anionic surfactant in the dispersion
- PS refers to the particle size of the particles in microns as determined by dynamic light scattering.
- OA Oleamide, m.p. 70 °C
- EA Esuracamide, m.p 80 °C
- BA behenamide, m.p.
- 112 C° is a C22-alkyl saturated primary fatty amide
- EBS ethylene bis-stearamide, m.p. 145° C
- OPA oleyl palmitamide, m.p. 60-66 °C
- SEA stearyl euracamide, m.p. 70-75 °C
- C4o-alkyl secondary fatty amide is a C4o-alkyl secondary fatty amide.
- the PO, N960, and the Amide were fed into a 25-mm diameter twin screw extruder using separate controlled rate feeders.
- the anionic surfactant (Oleic acid) was pumped into the melt zone of the extruder as a liquid using an Isco syringe pump at a feed rate of 3.4 mL/min.
- the PO, N960, and the Amide were forwarded through the extruder and melted to form an intermediate liquid melt material.
- the extruder temperature profile was ramped up to 150 °C. Water and 30% aq. KOH were mixed and fed to the extruder at an initial water introduction site after a uniform polymer melt was formed; then, dilution water was fed into the extruder.
- the extruder speed was 450 rpm for all samples except Comparative Example 5, where the extruder speed was 400 rpm.
- a backpressure regulator was used to adjust the pressure inside the extruder barrel to a pressure adapted to reduce steam formation, generally in the range of 2 MPa to 4 MPa. Each aqueous dispersion exited from the extruder and was filtered first through a 200-pm filter.
- the solids content of dispersions was measured using an infrared solids analyzer, and the volume mean particle size of the polymer particles was measured using a COULTERTM LS-230 particle size analyzer (Beckman Coulter Corporation, Fullerton, CA). Table 2 illustrates the MVTR and CoF for the examples and comparative examples.
- the coating thicknesses for each sample was 8 gsm.
- PO:N960:Amide refers to the w/w/w ratios of the polyolefin, the dispersant, and the fatty amide.
- the data show an improvement in MVTR for coatings containing primary fatty amides when compared with coatings containing either no amide additive or coatings containing secondary fatty amides.
- dynamic CoFs of 0.3 or less are acceptable; for other applications, CoFs of less than 0.2 are required.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to a method comprising the steps of a) applying onto paper a composition comprising an aqueous dispersion of poly-C2-C3-olefin particles, a dispersant, and a C5-C26-alkyl primary fatty amide; and b) drying the composition to form a coating having a coat weight in the range of from 1 g/m2 to 20 g/m2. The method of the present invention is useful for preparing coatings on paper with desirable moisture vapor transition rate and coefficient of friction properties.
Description
Method for Preparing a Polyolefin Coating for a Paper Substrate
Background of the Invention
The present invention relates to a method for preparing a thin polyolefin coating for a paper substrate. The coated paper has been found to have useful moisture vapor transmission rate properties.
Consumer demand for sustainable paper used in packaging is fueling interest in improving barrier properties and recyclability of coated paper. Barrier performance of paper is known to be enhanced with polyolefin coatings, which also provide heat-seal properties; still, attaining a coating areal density (coat weight) of < 10 g/m2 by application of an extruded polyolefin layer onto a paper substrate has been elusive. Achieving these ultra-low coat weights is especially important in flexible packaging applications, where paper substrates have a paper areal density (basis weight) of < 60 g/m2, and where the market requires > 85 wt% fiber recycling based on the mass of the article.
As disclosed in US 10,612,193 B2 (col. 2, Table 2) ultra-thin coatings can be prepared by applying a waterborne polyolefin emulsion onto the paper substrate, followed by curing; nevertheless, meeting targets for moisture vapor transmission rate (MVTR) and coefficient of friction (CoF) remain elusive. Accordingly, it would be an advance in the field of coated paper substrates to prepare a thin coating that meets the application requirements for MVTR and provides a recyclable package.
Summary of the Invention
The present invention addresses a need in the art by providing a method comprising the steps of a) applying onto paper a composition comprising an aqueous dispersion of poly-Ca-Cs-olefin particles, a dispersant, and a Cs-Cze-alkyl primary fatty amide; and b) drying the composition to form a coating having a coat weight in the range of from 1 g/m2 to 20 g/m2. The method of the present invention can be used to provide ultra-thin coatings on a paper substrate with advantageous moisture vapor transmission rate and coefficient of friction properties.
Detailed Description of the Invention
The present invention is a method comprising the steps of a) applying onto paper a composition comprising an aqueous dispersion of poly-C2-C3-olefin particles, a dispersant, and a Cs-C26-alkyl primary fatty amide; and b) drying the composition to form a coating having a coat weight in the range of from 1 g/m2 to 20 g/m2.
As used herein, “poly-C2-C3-olefin particles” refer to polyethylene particles, polypropylene particles, and poly(ethylene-propylene) copolymers particles. The polyethylene may be an ethylene-C4-Cio-a-olefin copolymer (i.e., linear low-density polyethylene) such as an ethylene- 1 -butene copolymer, an ethylene- 1— hexene copolymer, and an ethylene- 1 -octene copolymer. A commercially available linear low-density polyethylene is AFFINITY PL1280 LLDPE Ethylene-Octene Copolymer (A Trademark of The Dow Chemical Company or its Affiliates). The polyethylene may also be a high-density polyethylene, commercially available, for example, as DOW™ DMDA-8940 NT 7 HDPE Resin; or a low-density polyethylene. An example of a commercially available ethylene-propylene copolymer is VERSIFY™ 4200 Propylene-Ethylene Copolymer (Trademarks of The Dow Chemical Company or its Affiliates), and a commercially available polypropylene is Braskem 6D43 Random Copolymer. The particles, which are believed to contain the C2-C3-polyolefin and some amount of the dispersant and the primary fatty amide associated therewith, preferably have a volume mean particle size in the range of from 200 nm or from 300 nm to 5 pm or to 3 pm or to 1.5 pm, as measured by dynamic light scattering.
The dispersant is a copolymer of ethylene and a carboxylic acid monomer or a salt thereof. Examples of suitable dispersants include ethylene- acrylic acid copolymers, ethylene-methacrylic acid copolymers, and ethylene-itaconic acid copolymers, and lithium, sodium, and potassium salts thereof.
The weight-to-weight ratio of structural units of ethylene to carboxylic acid monomer or salt thereof is preferably in the range of from 95:5, more preferably from 90: 10, and most preferably from 85:15; to 70:30, more preferably to 75:25. As used herein, the term “structural unit” of the named monomer refers to the remnant of the monomer after polymerization. For example, a structural unit of methacrylic acid is as illustrated:
structural unit of methacrylic acid where the dotted lines represent the points of attachment of the structural unit to the polymer backbone.
Examples of commercially available dispersants include PRIMACOR™ 5980i Ethylene- Acrylic Acid Copolymer and NUCREL 960™ Ethylene- Methacrylic Acid Copolymer (Trademarks of The Dow Chemical Company or its Affiliates).
The C.5-C26-alkyl primary fatty amide may be linear or branched and may be saturated or partially unsaturated with one or two or three double bonds. The fatty amide may also be a Cio--C24-alkyl primary fatty amide or a Ci6-C22-alkyl primary fatty amide. Examples of suitable fatty amides include linear and branched Cis -alkyl mono-unsaturated fatty amides; linear and branched Cis-alkyl saturated fatty amides; linear and branched C22-alkyl mono-unsaturated fatty amides; and linear and branched C22-alkyl saturated fatty amides. The Cs-C26-alkyl primary fatty amide preferably has a melting point in the range of from 50 °C or from 65 °C to 115 °C or to 100 °C or to 90 °C.
The concentration of the poly-C2-C3-olefin particles less any associated dispersant or primary fatty amide is preferably in the range of from 40 or from 60 or from 70 weight percent, to 95 or to 90 weight percent, based on the weight of the polyolefin, the dispersant, and the Cs-C26-alkyl primary fatty amide. The concentration of the dispersant is preferably in the range of from 4 or from 9, or from 15 weight percent, to 50, or to 40, or to 30 weight percent, based on the weight of the polyolefin particles, the dispersant, and the C5-C26 -alkyl fatty amide. The concentration of the Cs-C26-alkyl primary fatty amide is preferably in the range of from 0.5 or from 1 to 5 or to 4 or to 3 weight percent, based on the weight of the polyolefin particles, the dispersant, and the C5-C26-alkyl fatty amide. The pH of the composition is preferably in the range of from 8 to 11. A neutralizing agent such as KOH is advantageously used to adjust the pH to the desired level.
The composition advantageously further comprises a stabilizing amount of an anionic surfactant such as a C10-C24 linear or branched alkyl or aralkyl carboxylate, sulfate, or phosphate; or a nonionic surfactant such as a secondary alcohol ethoxylate or an ethylene oxide propylene oxide
block copolymer surfactant. The composition is advantageously applied to a paper substrate with a drawdown bar, followed by removal of water, preferably at advanced temperatures as described in the next section.
It has been discovered that coat weights in the range of 1 g/m2, or from 2 g/m2 or from 5 g/m2 to 20 g/m2 or to 12 g/m2 or to 10 g/m2 can be achieved with desirable moisture vapor transmission rate (MVTR) and coefficient of friction (CoF) properties.
Method for Preparing Coated Substrates and Measuring Coat Weights
UPM Brilliant 62 Glassine Paper (basis wt. 62 g/m2) was coated with the polyolefin dispersion using a drawdown bar and dried in a forced air oven for 2 min at 100° C to a final coating areal density (coat weight) of 8 g/m2 (~ 8 to 9 pm coating thickness). Coat weights were measured by punching holes in coated and uncoated UPM paper with a circular die to form discs having a specified diameter (D cm). The coated discs (Wl) were weighed against the uncoated disc (W2) and the coat weights were calculated by the formula:
Moisture Vapor Transmission Rate Measurements
Moisture Vapor Transmission Rates (MVTRs) were determined in accordance with
ASTM E96/E96M. A coated paper sample was sealed to the open end of a permeability cup followed by exposure of the sample to a controlled temperature and humidity environment (typically, a humidity chamber). MVTR was determined based by measuring mass uptake for the cup as a function of time.
Dynamic Coefficient of Friction Measurements
The dynamic coefficients of friction (CoFs) were measured using a Texture Analyzer with a sliding friction rig in accordance with TAPPI T549. A piece of coated paper was affixed to the bottom of a sled weighing 200 g with the coated side facing down. Another piece of coated paper was affixed to a plane with coated side facing up. A string was attached to the sled and pulled so that the sled traversed the plane at the speed of 2.5 mm/s for at least 100 mm. The plateaued force Fd (unit: gram force) for the constant moving of the sled was recorded.
Dynamic CoFs were calculated as Fd/200.
Calculation of Degree of Neutralization
The degree of neutralization of the polyolefin dispersions was determined by the following equation:
56000 x W
DoN = 100 where W is the weight of the base added in g, EB is the equivalent weight of the base, Ai is the acid number of the ith component in units of mg KOH/g and the CD i is the weight fraction of the ith component in POD dispersion solid.
Examples
Table 1 illustrates the components and feed rates used to prepare Examples 1-4 and Comparative Examples 1 -5. Feed rates are shown parenthetically. The general procedure is shown following Table 1. PO refers to the polyolefin; Amide refers to the fatty amide; ITO., refers to the initial water rate; ILOd refers to the dilution water rate; Solids refers to the wt.% solids of the polyolefin the dispersant, the fatty amide, and the anionic surfactant in the dispersion; and PS refers to the particle size of the particles in microns as determined by dynamic light scattering.
PL1280 refers to AFFINITY™ PL 1280 LLDPE Ethylene- Octene Copolymer; V4200 refers to VERSIFY™ Ethylene-Propylene Copolymer; N960 refers to NUCREL™ N960 Ethylene- Methacrylic Acid Copolymer. OA (Oleamide, m.p. 70 °C) is a Cis-alkyl mono-unsaturated primary fatty amide; EA (Euracamide, m.p 80 °C) is a C22-alkyl mono-unsaturated primary fatty amide; BA (behenamide, m.p. 112 C°) is a C22-alkyl saturated primary fatty amide; EBS (ethylene bis-stearamide, m.p. 145° C) is a Css-alkyl secondary fatty amide; OPA (oleyl palmitamide, m.p. 60-66 °C) is a C34-alkyl secondary fatty amide; SEA (stearyl euracamide, m.p. 70-75 °C) is a C4o-alkyl secondary fatty amide.
The degree of neutralization for Comparative Examples 1-4 and Examples 1-6 was 75% and the degree of neutralization for Comparative Example 5 and Example 7 was 80%.
Table 1 - Components and Feed Rates for Examples
General Procedure for Preparation of Aqueous Dispersions of Polyolefin Dispersions Aqueous dispersions were prepared by the following general procedure:
The PO, N960, and the Amide (except for Comparative Examples 1 and 5) were fed into a 25-mm diameter twin screw extruder using separate controlled rate feeders. The anionic surfactant (Oleic acid) was pumped into the melt zone of the extruder as a liquid using an Isco syringe pump at a feed rate of 3.4 mL/min. The PO, N960, and the Amide were forwarded through the extruder and melted to form an intermediate liquid melt material.
The extruder temperature profile was ramped up to 150 °C. Water and 30% aq. KOH were mixed and fed to the extruder at an initial water introduction site after a uniform polymer melt was formed; then, dilution water was fed into the extruder. The extruder speed was 450 rpm for all samples except Comparative Example 5, where the extruder speed was 400 rpm. At the extruder outlet, a backpressure regulator was used to adjust the pressure inside the extruder barrel to a pressure adapted to reduce steam formation, generally in the range of 2 MPa to 4 MPa.
Each aqueous dispersion exited from the extruder and was filtered first through a 200-pm filter.
The solids content of dispersions was measured using an infrared solids analyzer, and the volume mean particle size of the polymer particles was measured using a COULTER™ LS-230 particle size analyzer (Beckman Coulter Corporation, Fullerton, CA). Table 2 illustrates the MVTR and CoF for the examples and comparative examples. The coating thicknesses for each sample was 8 gsm. PO:N960:Amide refers to the w/w/w ratios of the polyolefin, the dispersant, and the fatty amide.
The data show an improvement in MVTR for coatings containing primary fatty amides when compared with coatings containing either no amide additive or coatings containing secondary fatty amides. For certain applications, dynamic CoFs of 0.3 or less are acceptable; for other applications, CoFs of less than 0.2 are required.
Claims
1. A method comprising the steps of a) applying onto paper a composition comprising an aqueous dispersion of poly-C2-C3-olefin particles, a dispersant, and a Cs-C26-alkyl primary fatty amide; and b) drying the composition to form a coating having a coat weight in the range of from 1 g/m2 to 20 g/m2.
2. The method of Claim 1 wherein, based on the weight of the poly-C2-C3-olefin particles, the dispersant, and the C5-C26-alkyl primary fatty amide in the composition, the concentration of the polyolefin particles is in the range of from 40 to 95 weight percent; the concentration of the dispersant is in the range of from 4 to 50 weight percent; and the concentration of the C5-C26- alkyl primary fatty amide is in the range of from 0.5 to 5 weight percent.
3. The method of Claim 2 wherein the dispersant is an ethylene- acrylic acid copolymer or a salt thereof, or an ethylene-methacrylic acid copolymer or a salt thereof; and the Cs-C26-alkyl primary fatty amide is a Cw/C24-alkyl primary fatty amide; and wherein the composition is dried to form a coating with a coat weight in the range of from 5 g/m2 to 10 g/m2.
4. The method of Claim 3 wherein the Cio-C.24-alkyl primary fatty amide is a Ci6-C.22-alkyl primary fatty amide having a melting point in the range of from 50 °C to 115 °C, and the poly-C2-C3-olefin particles are ethylene-C4-Cio-a-olefin copolymer particles.
5. The method of Claim 4 wherein the ethylene-C4-Cio-a-olefin copolymer particles are ethylene- 1 -octene copolymer particles.
6. The method of Claim 3 wherein the Cio-C24-alkyl primary fatty amide is a Ci6-C22-alkyl primary fatty amide having a melting point in the range of from 50 °C to 115 °C, and the poly-C2-C3-olefin particles are polypropylene particles.
7. The method of 3 wherein the Cio-C24-alkyl primary fatty amide is a Ci6-C22-alkyl primary fatty amide having a melting point in the range of from 50 °C to 115 °C, and the poly-C2-C3-olefin particles are poly(ethylene-propylene) copolymers particles.
8. The method of Claim 2 wherein, based on the weight of the poly-C2-C3-olefin particles, the dispersant, and the Cs-C26-alkyl primary fatty amide, the concentration of the poly-C2-C3-olefin is in the range of from 60 to 90 weight percent; the concentration of the dispersant is in the range
of from 9 to 40 weight percent; and the concentration of the Cs-C26-alkyl primary fatty amide is in the range of from 1 to 4 weight percent.
9. The method of any of Claims 4 to 7 wherein, based on the weight of the poly-C2-C3-olefin particles, the dispersant, and the Ci6-C.22-alkyl primary fatty amide, the concentration of the poly-C2-C3-olefin is in the range of from 60 to 90 weight percent; the concentration of the dispersant is in the range of from 9 to 40 weight percent; and the concentration of the Ci6-C22-alkyl primary fatty amide is in the range of from 1 to 4 weight percent.
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US20180363248A1 (en) * | 2017-06-15 | 2018-12-20 | Dow Global Technologies Llc | Paper coated with a functional polyolefin film |
KR102006945B1 (en) * | 2019-02-07 | 2019-08-02 | 전인성 | Eco-friendly recyclable water-proof coating paper |
CN111748246A (en) * | 2019-03-28 | 2020-10-09 | Dic株式会社 | Coating agent, laminate coated with same, packaging material, and processed product |
WO2021225764A1 (en) * | 2020-05-05 | 2021-11-11 | Dow Global Technologies Llc | Paper coated with a functional polyolefin film |
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US20180363248A1 (en) * | 2017-06-15 | 2018-12-20 | Dow Global Technologies Llc | Paper coated with a functional polyolefin film |
US10612193B2 (en) | 2017-06-15 | 2020-04-07 | Dow Global Technologies Llc | Paper coated with a functional polyolefin film |
KR102006945B1 (en) * | 2019-02-07 | 2019-08-02 | 전인성 | Eco-friendly recyclable water-proof coating paper |
CN111748246A (en) * | 2019-03-28 | 2020-10-09 | Dic株式会社 | Coating agent, laminate coated with same, packaging material, and processed product |
WO2021225764A1 (en) * | 2020-05-05 | 2021-11-11 | Dow Global Technologies Llc | Paper coated with a functional polyolefin film |
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