WO2019156702A1 - Matériaux à base d'huiles siccatives - Google Patents

Matériaux à base d'huiles siccatives Download PDF

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Publication number
WO2019156702A1
WO2019156702A1 PCT/US2018/036445 US2018036445W WO2019156702A1 WO 2019156702 A1 WO2019156702 A1 WO 2019156702A1 US 2018036445 W US2018036445 W US 2018036445W WO 2019156702 A1 WO2019156702 A1 WO 2019156702A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
partially cured
polymer blend
binder composition
cured binder
Prior art date
Application number
PCT/US2018/036445
Other languages
English (en)
Inventor
William J. Kauffman
JR. Walter J. LEWICKI
Original Assignee
Kauffman William J
Lewicki Jr Walter J
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
Priority claimed from US15/891,803 external-priority patent/US10875971B2/en
Priority claimed from US15/986,195 external-priority patent/US10947406B2/en
Application filed by Kauffman William J, Lewicki Jr Walter J filed Critical Kauffman William J
Publication of WO2019156702A1 publication Critical patent/WO2019156702A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/005—Drying oils
    • 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
    • C08L91/005—Drying oils
    • 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
    • C08L91/04—Linoxyn
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
    • C09F7/00—Chemical modification of drying oils
    • C09F7/06—Chemical modification of drying oils by polymerisation

Definitions

  • the invention is directed to partially cured binder compositions comprising a reaction product of at least one drying oil and at least one multi-functional co-vulcanizing agent and their methods of manufacture.
  • Drying oils harden/cure after a period of exposure to air.
  • the oil hardens through a chemical reaction in which the components crosslink by action of oxygen - air oxidation.
  • Drying oils include but are not limited to natural oils such as linseed oil, Tung oil, sunflower oil, walnut oil, poppy oil, perilla oil, and air drying synthetic alkyd resins. These materials are utilized in coatings, paints, printing inks and flooring.
  • Linoleum flooring involves partially air oxidizing linseed oil until a select viscosity is obtained. This oxidation is done at elevated temperature and takes significant time to reach the desired viscosity. This partially pre-oxidized/partially cured material is called Lynoxyn.
  • Lynoxyn is then mixed with rosin, fillers and pigments and subsequently consolidated into a layer, typically on a backing material to form a flooring structure.
  • the flooring does not possess the desired physical properties and needs to be further oxidatively cured by“stoving” at slightly elevated temperature in circulating air.
  • This curing process takes considerable time such as 8-16 weeks before desired properties are obtained.
  • More rapid curing has advantages in coatings, paints and printing ink applications as well.
  • This invention describes the manufacture of partially cured binder compositions based upon modification of drying oils with at least one multi-functional co-vulcanizing agent.
  • the mixture of at least one drying oil and at least one multi-functional co vulcanizing agent further comprises at least one radical initiator and oxygen is removed from the composition.
  • the mixture is then reacted by heating at elevated temperature in inert conditions to produce the desired partially cured binder composition.
  • inerting gases commonly used are Carbon Dioxide, Argon, and Nitrogen. Inerting techniques may include purging, blanketing, and sparging depending upon the end result desired.
  • the mixture of at least one drying oil and at least one multi functional co-vulcanizing agent further comprises a siccative material and the mixture is reacted under normal oxidative conditions to a desired viscosity for the partially cured binder
  • the partially cured binder compositions of this invention can be used to produce products such as cured layers including filled or transparent coatings.
  • One preferred embodiment is the use in flooring products.
  • a transparent coating for use as a wear layer is described.
  • a printing ink is used in typical decorating process is described.
  • This invention describes the manufacture of partially cured binder compositions based upon modification of drying oils. Drying oils harden after a period of exposure to air. The oil hardens through a chemical reaction in which the components crosslink by action of oxygen - air oxidation. Drying oils include but are not limited to natural oils such as linseed oil, Tung oil, sunflower oil, walnut oil, poppy oil, perilla oil, and drying synthetic alkyd resins. Typically, these drying oils are partially reacted with oxygen until a desired viscosity is achieved for the polymer binder.
  • the binder compositions of this invention comprise the addition of a reactive multi-functional co-vulcanizing agent with the drying oil prior to forming the partially cured polymer binder. A partially cured binder composition is produced that offers material and process advantages.
  • At least one multi-functional co-vulcanizing agent can be co-reacted with at least one drying oil under oxidative conditions. Additionally, the multi-functional co- vulcanizing agent can be self-reacted under radical conditions if oxygen is not present.
  • Non limiting examples of multi-functional co-vulcanizing agents include triallyl cyanurate, triallyl isocyanurate, trimethanolpropane triallyl ether, pentaerythritol tetra allyl ether, or other poly functional materials that include an activated alpha methylene group adjacent a peroxide curable double or triple bond. These multi-functional co-vulcanizing agents can be monomeric or polymeric in nature and comprise at least two reactive functional groups.
  • the co-vulcanizing agent can be added from 1% up to 100% by weight of the drying oil depending upon the co-vulcanizing agent’s composition and processing conditions.
  • the co-vulcanizing agent is at least around 1%, at least around 5%, at least around 10%, at least around 15%, at least around 20%, at least around 25%, at least around 30%, at least around 35%, at least around 40%, at least around 45%, at least around 50%, by weight of the drying oil.
  • One embodiment has the co-vulcanizing agent at a 1 %-30% level.
  • the elements of this invention can be described by the following embodiments.
  • the oxidation of linseed oil to produce Lynoxyn is well known and has been the basis of the manufacture of Linoleum flooring.
  • One issue in the manufacture of linoleum is that once the Lynoxyn binder is compounded into a Linoleum formulation and processed into a flooring structure it requires additional oxidation for considerable time to cure and develop the necessary physical properties required to function as a resilient flooring layer or material. This is usually accomplished by stoving at slightly elevated temperatures with air flowing through the stoving equipment. Historically this could take up to 8 weeks to 16 weeks to reach desired curing.
  • At least one reactive multi-functional co-vulcanizing agent is added to at least one drying oil, i.e. linseed oil, and the mixture subjected to normal oxidative conditions until the desired viscosity is achieved producing a partially cured binder.
  • Siccatives and optionally peroxide can be added to the mixture to facilitate the reaction.
  • the reaction may be quenched as done in the normal linoleum process if desired.
  • linseed oil is utilized, this produces a modified Lynoxyn binder. Significantly shorter reaction time is required to obtain the desired viscosity for the modified Lynoxyn binder.
  • This modified binder composition is then processed into Linoleum and subjected to oxidative stoving conditions.
  • Additional siccative materials can be added to the modified Lynoxyn before oxidative curing.
  • the cure time to achieve desired properties is significantly reduced, such as, but not limited to, 2 weeks or less before the desired properties are obtained. It is understood that some stoving time or annealing time may still be desired to achieve desired properties, for example, improved dimensional stability of the final product, depending upon the formulation composition and process option selected.
  • the partially cured binder composition of the invention is combined with at least one polymer material to produce a polymer blend.
  • the partially cured binder produced by the normal oxygen oxidation process can be blended with at least one additional polymer composition to produce a polymer blend.
  • These blends can be a single phase, or multiple phases depending upon the polymer(s) selected.
  • the polymer selected can be either a thermoset or thermoplastic material.
  • the polymeric material(s) selected can be cured by the same mechanism as the partially cured binder composition.
  • the polymeric material(s) selected can be cured by a different mechanism than the partially cured binder composition, leading to polymer blend composition having potential for dual cure mechanisms.
  • a partially cured binder prepared by normal oxygen oxidation conditions can be mixed with other materials such as natural rubbers, unsaturated polyesters comprising renewable components, or other renewable based polymeric materials. These renewable blended compositions can be further cured by oxidative, radical or other known options to produce cured layers. Dual cure compositions are possible.
  • a polymer blend having 20% of the partially cured binder prepared by normal oxidative conditions and 80% Natural Rubber (NR) is prepared using an extruder.
  • a peroxide curative for the natural rubber is added and mixed into the polymer blend.
  • the polymer blend is extruded into a nip consisting of two rollers which forms a layer.
  • the layer is heated at elevated temperature to decompose the peroxide and cure the rubber. Subsequently, the cured layer is exposed to oxygen annealing that further cures the partially cured binder of this invention.
  • 80% epoxidized natural rubber (ENR), and 20% of the partially cured binder prepared by normal oxidation are compounded on a two roll mill.
  • the epoxy component of the ENR reacts with the partially cured binder enhancing compatibility.
  • a peroxide curative for the ENR is added and mixed into the polymer blend. After forming into a layer and curing at elevated temperature a polymer blend with good physical properties is obtained.
  • Blends with thermoplastic polymers are also possible. This includes traditional thermoplastic polymer as well as thermoplastic polymers comprising renewable components.
  • the partially cured binder composition is compatible with the thermoplastic polymer.
  • the partially cured binder composition is incompatible and produces a blend having at least two phases.
  • the phase of the partially cured binder composition is dispersed within the continuous phase of the thermoplastic polymer(s).
  • the partially cured binder composition can be cured to produce a polymer blend comprising at least one phase having a cured polymeric binder of the invention.
  • 20% of the partially cured binder composition produced by normal oxidation conditions is compounded with 80% polypropylene using extruder conditions of about 175C.
  • the polymer blend is extruded onto a double belted press, consolidated and cooled to form a layer.
  • the layer has a phase of the partially cured binder composition dispersed within a phase of polypropylene.
  • the partially cured binder continues to cure by oxygen oxidation.
  • a peroxide is added to a mixture of at least one multi-functional co-vulcanizing agent and at least one drying oil, and oxygen is removed. Typically, nitrogen is employed to maintain an inert environment. The mixture is stirred and heated to decompose the peroxide to cause the co-vulcanizing agent and drying oil to react increasing viscosity to produce a partially cured polymer binder composition. Siccatives can then be added to the binder composition to allow oxidative curing if desired. This partially cured polymer binder can be compounded with fdlers, fibers, pigments and other polymeric materials to produce
  • compositions that can be formed into layers which can be oxidatively cured resulting in layers. It is also possible to utilize polymeric materials to produce polymer blends that can be cured by alternate methods, leading to polymer blend compositions having potential for dual cure mechanisms. It is also possible to produce polymer blend compositions utilizing thermoplastic polymeric materials blended with the partially cured binder composition.
  • the partially cured binder composition obtained by decomposing a peroxide under inert conditions is further compounded with another peroxide, formed into a layer, and subsequently fully cured by heating to decompose the peroxide under inert conditions.
  • other materials such as fillers and fibers can be added. Natural fiber and in particular nano-cellulose are added to provide increased strength and flexibility to the layer. The final mixture is deaerated to remove oxygen.
  • One process option would be to use an extruder with deaeration and form a layer which is further cured in the presence of nitrogen.
  • the subsequent use of non-porous double belt presses to heat and cool one or more layers during curing is more efficient in retaining an oxygen free environment. Less nitrogen inerting gas is required in this method.
  • a partially cured binder prepared by decomposing a peroxide under inert conditions can be mixed with other materials such as natural rubbers, unsaturated polyesters from natural produced components, or other natural based materials. These blended compositions can be formed into layers and cured by radical or other known options to produce layers. Dual cure compositions are also possible. Blends with thermoplastic polymers are also possible.
  • the layers comprising the partially cured binder can be produced by traditional means.
  • a continuous extruder process is advantageous for those compositions described that use peroxide curing under inert conditions.
  • other materials such as particles or particles of the same material but having different color can be applied and processed into the layer to provide other visual effects.
  • One or more double belted presses in combination with particle scattering machines are used to form patterned linoleum flooring, desktop material, wall coverings and like products. Examples of belt surfaces include but are not limited to Teflon, silicone, stainless steel, polypropylene paper, and the like.
  • engraved or etched steel plates and belts produce unique multilevel texturing on the surfaces of the cured layer.
  • an extended press nip having engraved components produces three dimensionalities to one or both sides of the binder layer which enhances design appeal and increases wear surface performance.
  • a double belted press or plates having engraved or etched designs is applied to a design on the partially cured binder layer.
  • the design can be printed by rotogravure, screen, lithographic, and digital printing systems.
  • a design can be applied by many other decorating methods which are well known to those skilled in the art.
  • the preferred printing technique is digital printing and more specifically inkjet printing.
  • the engraved design of the belt or plate is mechanically embossed into a design on the binder layer. If desired, matching the size of the embossed design to the print (MEIR) is achieved by making adjustments at the digital printer or by making temperature adjustments to equipment and/or material during manufacture. Natural materials contain grain, fissures, particles and the like.
  • the layer is formed on a backing material.
  • the layer can be cured by heating under inert conditions to initiate radical cross-linking. The temperature selected is dependent upon the initiator used, and the desired kinetics of radical generation. More than one radical generator can be utilized in the formulation. It is understood that the layer can be formed onto known substrates: such as woven and non- woven backings containing natural and synthetic materials, felt or glass backings, stainless steel, Teflon or silicone belts, and/or release paper.
  • embossed release paper, design carrying belts or engraved plates can be used to impart 3-D dimensionality to one or both sides of the layer. It is also understood that other well-known options for heating and curing the layer may be used, such as the use of double stainless steel and Teflon-coated double belt presses.
  • inert curing conditions are not required.
  • applying an impermeable layer, to the surface of the layer inhibits oxygen from penetrating into the layer during the curing process.
  • the impermeable layer may be a transparent wear layer, a decorative layer, and /or a combination of a wear layer and decorative layer.
  • the layer is applied by lamination, coating prior to curing, or a combination of lamination and/or coating prior to final cure. The methods used by those skilled in the art to make a surface of a substrate impervious to oxygen and or moisture are well known.
  • the layer comprising the partially cured binder can also contain a blowing agent which expands the layer when heated.
  • the partially cured binder layer can be printed with one or more of the design inks containing a foam inhibitor.
  • A“chemically embossed in register” structure (CEIR) is produced after application of the wear layer and application of a higher temperature, during which the blowing agent is activated to form a foam.
  • the areas of ink containing an inhibitor retards the expansion of the blowing agent: Ref:
  • the partially cured binder composition of this invention can be used to produce surface coverings that have three dimensionality (embossing) on one or both sides of the cured layer comprising the binder composition.
  • the embossing can be a random texture or in register with a printed design.
  • the partially cured binder composition can be formulated into non-traditional formulations to produce new materials for use as a flooring layer or other applications.
  • the partially cured binder composition without opaque fillers can be processed into a transparent/translucent coating or ink, and subsequently cured using oxidative or radical techniques, including radiation. Radiation techniques include, but are not limited to, e- beam and UV curing; forms of electromagnetic radiation that enhance cure of polymeric compositions.
  • the binder composition can incorporate aluminum oxide, ceramic, or other hard particles to improve wear surface performance.
  • a UV initiator is added to the transparent coating composition and the applied coating is subsequently UV cured.
  • the transparent, cured coating functions as a wear layer for a resilient material.
  • the binder with or without fine abrasion resistant particles can be used as an ink or coating for non-resilient surfaces such as wood, tile, painted metal and the like.
  • colorants can be added to the partially cured binder composition and be used for decorative purposes.
  • the colorant/binder composition functions as an ink in printing.
  • the decorative ink can be cured using oxidative or radical techniques, including radiation.

Abstract

La présente invention concerne la préparation de compositions de liant partiellement durcies basées sur la modification d'huiles siccatives par au moins un agent de covulcanisation multifonctionnel. Les compositions de liant partiellement durcies peuvent être mélangées avec des matériaux polymères pour préparer des mélanges de polymères. Ces mélanges de polymères peuvent être utilisés pour produire des produits tels que des couches solides durcies. L'invention concerne également des procédés de préparation des compositions de liant partiellement durcies et des couches solides durcies.
PCT/US2018/036445 2018-02-08 2018-06-07 Matériaux à base d'huiles siccatives WO2019156702A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US15/891,803 US10875971B2 (en) 2017-06-13 2018-02-08 Materials based on drying oils
US15/891,803 2018-02-08
US15/986,195 2018-05-22
US15/986,195 US10947406B2 (en) 2017-06-13 2018-05-22 Materials based on drying oils

Publications (1)

Publication Number Publication Date
WO2019156702A1 true WO2019156702A1 (fr) 2019-08-15

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Application Number Title Priority Date Filing Date
PCT/US2018/036445 WO2019156702A1 (fr) 2018-02-08 2018-06-07 Matériaux à base d'huiles siccatives

Country Status (1)

Country Link
WO (1) WO2019156702A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2398670A (en) * 1946-04-16 Modified rosin ester-drying oil var
US2467912A (en) * 1949-04-19 Modified drying oils and process
US3293094A (en) 1965-12-20 1966-12-20 Congoleum Nairn Inc Textured foam processes
US3365353A (en) 1965-05-11 1968-01-23 Armstrong Cork Co Chemical embossing of foamed decorative surface covering
US5961903A (en) 1997-02-20 1999-10-05 Mannington Mills, Inc. Method of making a surface covering having a natural appearance
WO2017079376A1 (fr) * 2015-11-02 2017-05-11 Kauffman William J Matériaux à base d'huiles siccatives

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2398670A (en) * 1946-04-16 Modified rosin ester-drying oil var
US2467912A (en) * 1949-04-19 Modified drying oils and process
US3365353A (en) 1965-05-11 1968-01-23 Armstrong Cork Co Chemical embossing of foamed decorative surface covering
US3293094A (en) 1965-12-20 1966-12-20 Congoleum Nairn Inc Textured foam processes
US5961903A (en) 1997-02-20 1999-10-05 Mannington Mills, Inc. Method of making a surface covering having a natural appearance
WO2017079376A1 (fr) * 2015-11-02 2017-05-11 Kauffman William J Matériaux à base d'huiles siccatives

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