WO2021086779A1 - Elastic film laminates with film made in a calendaring process - Google Patents

Elastic film laminates with film made in a calendaring process Download PDF

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Publication number
WO2021086779A1
WO2021086779A1 PCT/US2020/057326 US2020057326W WO2021086779A1 WO 2021086779 A1 WO2021086779 A1 WO 2021086779A1 US 2020057326 W US2020057326 W US 2020057326W WO 2021086779 A1 WO2021086779 A1 WO 2021086779A1
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WO
WIPO (PCT)
Prior art keywords
composition
styrene
elastic film
fabric
equal
Prior art date
Application number
PCT/US2020/057326
Other languages
French (fr)
Inventor
Ketan Shah
Cesar Cruz
Original Assignee
Avient Corporation
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 Avient Corporation filed Critical Avient Corporation
Priority to EP20881147.1A priority Critical patent/EP4048733A4/en
Priority to US17/772,413 priority patent/US20220379595A1/en
Priority to CN202080090411.8A priority patent/CN114929803A/en
Publication of WO2021086779A1 publication Critical patent/WO2021086779A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/156—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is calendered and immediately laminated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/24—Calendering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/14—Mixture of at least two fibres made of different materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/756—Refurbishable, i.e. marks or scratches can be removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing
    • B32B2437/02—Gloves, shoes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2535/00—Medical equipment, e.g. bandage, prostheses, catheter
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    • B32B2605/00—Vehicles

Definitions

  • This invention relates to elastic film laminates made in a calendaring process and capable of being calendared with a fabric layer.
  • the present invention discloses a composition for calendaring, where the composition has a fabric and an elastic film component including a styrenic block copolymer, an oil, and optional additives.
  • the elastic film is adjacent to the fabric during and after the calendaring process.
  • the styrenic block copolymer is may be styrene- ethylene- butylene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene- ethylene/ propyl ene- styrene, styrene-i sobutyl ene- styrene, styrene-butadi ene- styrene, styrene-i soprene- styrene, or combinations of two or more thereof.
  • the fabric of the composition may be cotton, polyester or combinations or two or more thereof.
  • the invention is an article made from the calendared composition.
  • the article may be apparel, footwear, furniture or furniture covering, drapery, or any other suitable object.
  • the invention also discloses a method for manufacturing the composition.
  • the film could be sandwiched between two fabric layers, i.e., fabric - film- fabric.
  • the composition could include a fabric with the film on one side or two sides.
  • the film could have fabric only on one side.
  • the invention could be made with standard calendaring process technology.
  • melt index at 190°C and 230°C of the elastic formulations were measured to determine the physical properties of the assembly. If the melt index is below 4 grams/10 minutes at 190°C and less than 35 grams/10 minutes at 230°C, the elastic formulation showed very good cohesive strength. If, on the other hand, the melt indices were greater than 5 grams/10 minutes at 190°C, and greater than 39 grams/10 minutes at 230°C, the elastic formulation showed poor melt strength and cohesive strength. [00015] Once again, the melt index range between 4 and 5 grams/10 minutes at 190 C and between 35-39 grams/10 min at 230°C appear to be borderline case.
  • melt indices at 190°C for the elastic film formulation was less than 4 grams/10 minutes at 190°C, and below 35 grams/10 minutes at 230°C, such a formulation would make a film that will demonstrate peel force from the stainless steel plate at room temperature to be below 3 lbf, and will remain bonded with the fabric.
  • melt indices at 190°C for the elastic film formulation was greater than 5 grams/10 minutes at 190°C, and greater than 39 grams/10 minutes at 230°C, such formulations would make films that would demonstrate peel strength greater than 4 lbf, and will have poor cohesive strength.
  • the range of melt index between 4-5 grams/10 min at 190°C, and between 35-39 grams/10 min at 230°C appears to be a closer call by which the films made of such formulations will demonstrate peel force between 3-4 lbf, and will sometimes peel cleanly from the stainless steel rolls, and sometimes peel with cohesive failure.
  • a film is made of the elastic formulation that meets the following criteria, the film will demonstrate clean peel from the stainless steel rolls at 300- 400°F, and cleanly transfer onto the fabric without cohesive failure in the calendaring process: (1) melt index at 190°C below 4 grams/10 min; (2) melt index at 230°C below 35 grams/10 min; and (3) peel force from the stainless steel plates at room temperature to be between 0-3 lbf.
  • a film is made of the elastic formulation that meets the following criteria, the film will demonstrate cohesive failure with the stainless steel rolls at 300-400°F, and unevenly transfer onto the fabric with cohesive failure and melt fracture in the calendaring process: (1) melt index at 190°C greater than 5 grams/10 min; (2) melt index at 230°C above 39 grams/10 min; and (3) peel force from the stainless steel plates at room temperature to be greater than 4 lbf.
  • the film will sometimes demonstrate clean peel from the stainless rolls at 300-400°F, and sometimes cleanly transfer onto the fabric without cohesive failure in the calendaring process: (1) melt index at 190°C between 4-5 grams/10 min; (2) melt index at 230°C between 35-39 grams/10 min; and (3) peel force from the SS plates at room temperature to be between 3-4 lbf.
  • the elastic film portion of the invention may include a polymer, an oil, and optional additives.
  • Suitable polymers includes thermoplastic elastomers other than thermoplastic polyurethanes, such as styrenic block copolymers, thermoplastic vulcanizates, polyolefin elastomers, copolyesters, and combinations thereof.
  • Non-limiting examples of suitable styrenic block copolymers include styrene-ethylene/butylene-styrene (SEBS), styrene-ethylene/propylene- styrene (SEPS), styrene-ethylene/ethylene/propylene-styrene (SEEPS), styrene- isobutylene- styrene (SIBS), styrene-butadiene-styrene (SBS), styrene-isoprene- styrene (SIS), and combinations thereof.
  • SEBS styrene-ethylene/butylene-styrene
  • SEPS styrene-ethylene/propylene- styrene
  • SEEPS styrene-ethylene/ethylene/propylene-styrene
  • SIBS styrene-isoprene- styrene
  • SIS
  • Non-limiting examples of suitable copolymers include block copolymers composed from repeating soft segments of aliphatic polyether or aliphatic polyester and hard segments of aromatic polyester.
  • the polymer may be present in any appropriate amount, including, but not limited to approximately 25 wt. % to approximately 75 wt. %; approximately 30 wt. % to approximately 70 wt. %; approximately 35 wt. % to approximately 65 wt. %; approximately 40 wt. % to approximately 60 wt. %; and approximately 45 wt. % to approximately 55 wt. %.
  • Any suitable oil e.g., mineral oil, vegetable oil, synthetic oil, may be used. Specific examples of oil components are detailed in the Examples section below.
  • the oil may be present in any appropriate amount, including, but not limited to approximately 20 wt. % to approximately 35 wt. %; approximately 25 wt. % to approximately 30 wt. %; and approximately 27 wt. % to approximately 29 wt. %.
  • Suitable optional additives include conventional or commercially available plastics additives. Those skilled in the art of thermoplastics compounding, without undue experimentation, can select suitable additives from available references, for example, E.W. Flick, “Plastics Additives Database,” Plastics Design Library (Elsevier 2004).
  • Optional additives can be used in any amount that is sufficient to obtain a desired processing or performance property for the elastic film portion of the composition and/or the article molded therefrom.
  • the amount should not be wasteful of the additive nor detrimental to the processing or performance of the elastic film and/or the article molded therefrom.
  • Non-limiting examples of optional additives include adhesion promoters; anti-fogging agents; antioxidants; anti-static agents; biocides (antibacterials, fungicides, and mildewcides); colorants including pigments and dyes; dispersants; fillers and extenders; fire and flame retardants and smoke suppressants; hardness adjusters; impact modifiers; initiators; lubricants; micas; mold release agents; oils and plasticizers; processing aids; secondary polymers; silanes, titanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; and waxes.
  • adhesion promoters include adhesion promoters; anti-fogging agents; antioxidants; anti-static agents; biocides (antibacterials, fungicides, and mildewcides); colorants including pigments and dyes; dispersants; fillers and extenders; fire and flame retardants and smoke suppressants; hardness adjusters; impact modifier
  • the elastic film further include one or more of antioxidants and stabilizers; colorants; mold release agents; ultraviolet light absorbers; and combinations thereof.
  • Plasticizer can be used, for example, to adjust softness and/or improve flow or other properties of the polymer compound.
  • Any conventional oil capable of plasticizing styrenic block copolymer such as mineral oil, vegetable oil, synthetic oil, etc.
  • oils include those available under the PURETOL 380 brand from Petro-Canada, and those available under the PRIMOL 382 brand from ExxonMobil.
  • Preparation of polymer compounds of the disclosed invention is uncomplicated once the proper ingredients have been selected. The compound can be made in batch or continuous operations.
  • Mixing in a continuous process typically occurs in an extruder that is elevated to a temperature that is sufficient to melt the polymer matrix with addition of all additives at the feed-throat, or by injection or side-feeders downstream.
  • Extruder speeds can range from about 200 to about 700 revolutions per minute (rpm), for example, from about 250 rpm to about 350 rpm.
  • rpm revolutions per minute
  • the output from the extruder is pelletized for later processing into thermoplastic articles.
  • thermoplastic elastomer compounds of the disclosed invention are molded by injection molding processes into thermoplastic articles.
  • composition of the disclosed invention can be useful for making any type of fabric application including those that requires resistant to staining and damaging from food, drinks, oil, dirt, cleaners, and other related items.
  • composition of the disclosed invention have potential for use in applications in many different industries, including but not limited to: home decor; furniture; apparel and footwear; automotive and transportation; consumer products; electronics; healthcare and medical; household; and other industries or applications benefiting from the unique combination of properties.
  • composition of the present invention can be especially useful for making drapery, furniture, fabric covering for automobile seats, as well as clothing and footwear.

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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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Disclosed is a process for creating an elastic film or sheet by calendaring a composition, including a polymer and a fabric. The composition may include a polymer, a cotton, or a combination of both. The calendared composition can form tough, flexible films and sheets. The film and sheet can have optical and physical properties that make them suitable as a replacement for some PVC films. Also disclosed is a composition for calendaring including a fabric and a polymer.

Description

ELASTIC FILM LAMINATES WITH FILM MADE IN A CALENDARING PROCESS
CLAIM OF PRIORITY
[0001] This application claims the benefit of U.S. Provisional Patent
Application Serial No. 62/926,533 bearing Attorney Docket Number 12019014 and filed on October 27, 2019, which is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to elastic film laminates made in a calendaring process and capable of being calendared with a fabric layer.
BACKGROUND OF THE INVENTION
[0003] Demand exists for a material that can replace the polyvinyl chloride containing fabric used in products such as drapery or fabric coverings for furniture.
SUMMARY OF THE INVENTION
[0004] The present invention discloses a composition for calendaring, where the composition has a fabric and an elastic film component including a styrenic block copolymer, an oil, and optional additives. The elastic film is adjacent to the fabric during and after the calendaring process.
[0005] The styrenic block copolymer is may be styrene- ethylene- butylene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene- ethylene/ propyl ene- styrene, styrene-i sobutyl ene- styrene, styrene-butadi ene- styrene, styrene-i soprene- styrene, or combinations of two or more thereof. [0006] The fabric of the composition may be cotton, polyester or combinations or two or more thereof. [0007] In an embodiment, the invention is an article made from the calendared composition. The article may be apparel, footwear, furniture or furniture covering, drapery, or any other suitable object.
[0008] The invention also discloses a method for manufacturing the composition.
[0009] Features of the invention will become apparent with reference to the following embodiments. There exist various refinements of the features noted in relation to the above-mentioned aspects of the disclosed invention. Additional features may also be incorporated in the above-mentioned aspects of the disclosed invention. These refinements and additional features may exist individually or in any combination. For instance, various features discussed below in relation to any of the described aspects of the invention may be incorporated into any of the described aspects of the invention alone or in any combination.
EMBODIMENTS OF THE INVENTION
[00010] The following methodology was invented to develop and screen materials that would make uniform film in the calendaring process with good melt strength and cohesive strength, and transfer on to fabric without cohesive failure onto the SS rolls.
[00011] First, uniform 10 mil films were made in a Brabender™ machine using film die. The film was then sandwiched between a stainless steel plate on one side, and polyester or cotton fabric on the other side, forming a layered assembly. Next, the layered assembly was then pre-heated to 300°F in a compression molding machine for 60 seconds without adding any pressure, and subsequently pressed between the two plates by closing them under 25 PSI pressure for 15 seconds. This method was used replicate the calendaring process. In an embodiment, the film could be sandwiched between two fabric layers, i.e., fabric - film- fabric. In an embodiment, the composition could include a fabric with the film on one side or two sides. In an embodiment, the film could have fabric only on one side. In an embodiment, the invention could be made with standard calendaring process technology.
[00012] The assembly was then taken out and while hot, the fabric was pulled by hand to evaluate if the elastic film detached from the stainless steel plates without cohesive failure and stayed attached to the fabric, making a good laminate. If the film successfully stayed attached to the fabric without cohesive failure, it would mean that the formulation of the film would make a good laminate in the calendaring process. This type of experimentation represents a qualitative evaluation of the elastic film in regards to its bonding with fabric, which demonstrated sufficient cohesive strength to prevent ripping.
[00013] In order to quantify the above process, and be able to predict its performance in the calendaring process, the assembly was cooled to room temperature as it came out of the compression-molding machine, and then carried out 90-degree peel test in Instron™ machine. If the film peeled without cohesive failure from the stainless steel plate, remained attached to the fabric, and if the peel force was under 3 lbf at room temperature, the film material will detach from the stainless steel rolls in the calendaring process at 300-400°F, without cohesive failure and make a good laminate in the calendaring process. If however, the peel force was greater than 4 lbf at room temperature, it would indicate cohesive failure with poor melt strength. The range of peel force between 3 and 4 lbf appears to be a borderline case, where, depending on other criteria the film demonstrated good cohesive strength.
[00014] The melt index at 190°C and 230°C of the elastic formulations were measured to determine the physical properties of the assembly. If the melt index is below 4 grams/10 minutes at 190°C and less than 35 grams/10 minutes at 230°C, the elastic formulation showed very good cohesive strength. If, on the other hand, the melt indices were greater than 5 grams/10 minutes at 190°C, and greater than 39 grams/10 minutes at 230°C, the elastic formulation showed poor melt strength and cohesive strength. [00015] Once again, the melt index range between 4 and 5 grams/10 minutes at 190 C and between 35-39 grams/10 min at 230°C appear to be borderline case. In summary, if the melt indices at 190°C for the elastic film formulation was less than 4 grams/10 minutes at 190°C, and below 35 grams/10 minutes at 230°C, such a formulation would make a film that will demonstrate peel force from the stainless steel plate at room temperature to be below 3 lbf, and will remain bonded with the fabric.
[00016] If, on the other hand, if the melt indices at 190°C for the elastic film formulation was greater than 5 grams/10 minutes at 190°C, and greater than 39 grams/10 minutes at 230°C, such formulations would make films that would demonstrate peel strength greater than 4 lbf, and will have poor cohesive strength. The range of melt index between 4-5 grams/10 min at 190°C, and between 35-39 grams/10 min at 230°C appears to be a closer call by which the films made of such formulations will demonstrate peel force between 3-4 lbf, and will sometimes peel cleanly from the stainless steel rolls, and sometimes peel with cohesive failure.
[00017] If a film is made of the elastic formulation that meets the following criteria, the film will demonstrate clean peel from the stainless steel rolls at 300- 400°F, and cleanly transfer onto the fabric without cohesive failure in the calendaring process: (1) melt index at 190°C below 4 grams/10 min; (2) melt index at 230°C below 35 grams/10 min; and (3) peel force from the stainless steel plates at room temperature to be between 0-3 lbf.
[00018] If a film is made of the elastic formulation that meets the following criteria, the film will demonstrate cohesive failure with the stainless steel rolls at 300-400°F, and unevenly transfer onto the fabric with cohesive failure and melt fracture in the calendaring process: (1) melt index at 190°C greater than 5 grams/10 min; (2) melt index at 230°C above 39 grams/10 min; and (3) peel force from the stainless steel plates at room temperature to be greater than 4 lbf. [00019] If a film is made of the elastic formulation that meets the following criteria, the film will sometimes demonstrate clean peel from the stainless rolls at 300-400°F, and sometimes cleanly transfer onto the fabric without cohesive failure in the calendaring process: (1) melt index at 190°C between 4-5 grams/10 min; (2) melt index at 230°C between 35-39 grams/10 min; and (3) peel force from the SS plates at room temperature to be between 3-4 lbf.
[00020] The elastic film portion of the invention may include a polymer, an oil, and optional additives.
[00021] Suitable polymers includes thermoplastic elastomers other than thermoplastic polyurethanes, such as styrenic block copolymers, thermoplastic vulcanizates, polyolefin elastomers, copolyesters, and combinations thereof. [00022] Non-limiting examples of suitable styrenic block copolymers include styrene-ethylene/butylene-styrene (SEBS), styrene-ethylene/propylene- styrene (SEPS), styrene-ethylene/ethylene/propylene-styrene (SEEPS), styrene- isobutylene- styrene (SIBS), styrene-butadiene-styrene (SBS), styrene-isoprene- styrene (SIS), and combinations thereof.
[00023] Non-limiting examples of suitable copolymers include block copolymers composed from repeating soft segments of aliphatic polyether or aliphatic polyester and hard segments of aromatic polyester.
[00024] The polymer may be present in any appropriate amount, including, but not limited to approximately 25 wt. % to approximately 75 wt. %; approximately 30 wt. % to approximately 70 wt. %; approximately 35 wt. % to approximately 65 wt. %; approximately 40 wt. % to approximately 60 wt. %; and approximately 45 wt. % to approximately 55 wt. %.
[00025] Any suitable oil, e.g., mineral oil, vegetable oil, synthetic oil, may be used. Specific examples of oil components are detailed in the Examples section below.
[00026] The oil may be present in any appropriate amount, including, but not limited to approximately 20 wt. % to approximately 35 wt. %; approximately 25 wt. % to approximately 30 wt. %; and approximately 27 wt. % to approximately 29 wt. %. [00027] Suitable optional additives include conventional or commercially available plastics additives. Those skilled in the art of thermoplastics compounding, without undue experimentation, can select suitable additives from available references, for example, E.W. Flick, “Plastics Additives Database,” Plastics Design Library (Elsevier 2004).
[00028] Optional additives can be used in any amount that is sufficient to obtain a desired processing or performance property for the elastic film portion of the composition and/or the article molded therefrom. The amount should not be wasteful of the additive nor detrimental to the processing or performance of the elastic film and/or the article molded therefrom.
[00029] Non-limiting examples of optional additives include adhesion promoters; anti-fogging agents; antioxidants; anti-static agents; biocides (antibacterials, fungicides, and mildewcides); colorants including pigments and dyes; dispersants; fillers and extenders; fire and flame retardants and smoke suppressants; hardness adjusters; impact modifiers; initiators; lubricants; micas; mold release agents; oils and plasticizers; processing aids; secondary polymers; silanes, titanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; and waxes.
[00030] In some embodiments, the elastic film further include one or more of antioxidants and stabilizers; colorants; mold release agents; ultraviolet light absorbers; and combinations thereof.
[00031] Optional Plasticizer
[00032] Plasticizer can be used, for example, to adjust softness and/or improve flow or other properties of the polymer compound.
[00033] Any conventional oil capable of plasticizing styrenic block copolymer, such as mineral oil, vegetable oil, synthetic oil, etc., can be used in the present invention. Examples of commercially available oils include those available under the PURETOL 380 brand from Petro-Canada, and those available under the PRIMOL 382 brand from ExxonMobil. [00034] Processing and Methods of Making Elastic Film Composition [00035] Preparation of polymer compounds of the disclosed invention is uncomplicated once the proper ingredients have been selected. The compound can be made in batch or continuous operations.
[00036] Mixing in a continuous process typically occurs in an extruder that is elevated to a temperature that is sufficient to melt the polymer matrix with addition of all additives at the feed-throat, or by injection or side-feeders downstream. Extruder speeds can range from about 200 to about 700 revolutions per minute (rpm), for example, from about 250 rpm to about 350 rpm. Typically, the output from the extruder is pelletized for later processing into thermoplastic articles.
[00037] Processing techniques are described in available references, for example, Dominick V. Rosato et al., Plastics Design Handbook (Springer 2013). [00038] In some embodiments, thermoplastic elastomer compounds of the disclosed invention are molded by injection molding processes into thermoplastic articles.
[00039] Further aspects of the invention are directed to calendared articles made by calendaring processes.
USEFULNESS OF THE INVENTION
[00040] The composition of the disclosed invention can be useful for making any type of fabric application including those that requires resistant to staining and damaging from food, drinks, oil, dirt, cleaners, and other related items.
[00041] The calendared composition of the disclosed invention have potential for use in applications in many different industries, including but not limited to: home decor; furniture; apparel and footwear; automotive and transportation; consumer products; electronics; healthcare and medical; household; and other industries or applications benefiting from the unique combination of properties. [00042] In some embodiments, the composition of the present invention can be especially useful for making drapery, furniture, fabric covering for automobile seats, as well as clothing and footwear.
EXAMPLES
[00043] Non-limiting examples of various embodiments of the disclosed invention are provided.
Table 1. Formulation of Examples
Figure imgf000010_0001
Table 2. Formulation of Examples
Figure imgf000011_0001
Table 3. Formulation of Examples
Figure imgf000012_0001
Table 4. Formulation of Examples
Figure imgf000013_0001
Table 5. Formulations of Examples
Figure imgf000014_0001
Table 6. Formulations of Examples
Figure imgf000015_0001
Table 7. Formulations of Examples
Figure imgf000016_0001
Table 8. Formulations of Examples
Figure imgf000017_0001
Table 9. Formulations of Examples
Figure imgf000018_0001
Table 10. Formulations of Examples
Figure imgf000019_0001
Table 11. Formulations of Examples
Figure imgf000020_0001
Table 12. Formulations of Examples
Figure imgf000021_0001
Table 13. Ingredients
Figure imgf000022_0001
Table 14. Peel Test Results
Figure imgf000023_0001
Table 15. Shore A Hardness
Figure imgf000024_0001
[00044] Without undue experimentation, those having ordinary skill in the art can utilize the written description, including the Examples, to make and use aspects of the disclosed invention.
[00045] All documents cited in the Embodiments of the Invention are incorporated herein by reference in their entirety unless otherwise specified. The citation of any document is not to be construed as an admission that it is prior art with respect to the disclosed invention.
[00046] While particular embodiments of the disclosed invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. The appended claims are intended to cover all such changes and modifications within the scope of the disclosed invention.

Claims

WHAT IS CLAIMED IS:
1. A composition for calendaring, comprising:
(a) an elastic film comprising: a styrenic block copolymer; an oil; and optional additives;
(b) a fabric; wherein the elastic film is positioned adjacent to the fabric.
2. The composition of claim 1, wherein the styrenic block copolymer is selected from a group consisting of styrene- ethylene-butylene-styrene, styrene- ethylene-propylene-styrene, styrene-ethylene-ethylene/propylene-styrene, styrene-isobutylene-styrene, styrene-butadiene-styrene, styrene-isoprene- styrene, or combinations thereof.
3. The composition of any of claims 1-2, wherein the fabric is selected from the group consisting of cotton, polyester, or combinations thereof.
4. The composition of any of claims 1-3, wherein the elastic film further comprises greater than or equal to 25 wt. % and less than or equal to 75 wt. % styrenic block copolymer.
5. The composition of any of claims 1-4, wherein the elastic film further comprises greater than or equal to 40 wt. % and less than or equal to 70 wt. % styrenic block copolymer.
6. The composition of any of claims 1-5, wherein the elastic film further comprises greater than or equal to 20 wt. % and less than or equal to 35 wt. % oil.
7. The composition of any of claims 1-6, wherein the elastic film further comprises greater than or equal to 25 wt. % and less than or equal to 30 wt. % oil.
8. The composition of any of claims 1-7, wherein the elastic film is positioned between and adjacent to a first fabric and a second fabric.
9. The composition of claim 8, wherein the first fabric comprises a first material and the second fabric comprises a second material.
10. The composition of claim 9, wherein the first material is the same as the second material.
11. The composition of claim 9, wherein the first material is different than the second material.
12. The composition of any of claims 1-11, wherein the melt indices of the elastic film at 190°C is below 4 grams/10 minutes.
13. The composition of any of claims 1-11, wherein the melt indices of the elastic film at 230°C is approximately between 35-39 grams/10 minutes.
14. The composition of any of claims 1-13, wherein the peel force for the elastic film from stainless steel plates at room temperature is approximately between 0-3 lbf.
15. An article comprising the composition of claim 1, wherein the article is selected from the group consisting of apparel, footwear, furniture, and drapery.
16. A method for manufacturing a composition comprising the steps of: preparing an elastic film composition comprising a styrenic block copolymer, an oil, and optional additives, wherein the elastic film has a first side and an opposite second side; sandwiching the elastic film composition between a first stainless steel plate on the first side and fabric on the second side to create a layered assembly; pre-heating the layered assembly; pressing the layered assembly between the first stainless steel plate and a second stainless steel plate; and removing the fabric and elastic film assembly from the stainless steel plate.
PCT/US2020/057326 2019-10-27 2020-10-26 Elastic film laminates with film made in a calendaring process WO2021086779A1 (en)

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