WO2006036409A2 - Process for coating extruded thermoplastic substrates and objects formed thereby - Google Patents

Process for coating extruded thermoplastic substrates and objects formed thereby Download PDF

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Publication number
WO2006036409A2
WO2006036409A2 PCT/US2005/030320 US2005030320W WO2006036409A2 WO 2006036409 A2 WO2006036409 A2 WO 2006036409A2 US 2005030320 W US2005030320 W US 2005030320W WO 2006036409 A2 WO2006036409 A2 WO 2006036409A2
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WO
WIPO (PCT)
Prior art keywords
pvc
coating
coat
weatherable
polymeric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2005/030320
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French (fr)
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WO2006036409A3 (en
Inventor
Kevin Hanrahan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema Inc
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Arkema Inc
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Filing date
Publication date
Application filed by Arkema Inc filed Critical Arkema Inc
Priority to CN2005800313819A priority Critical patent/CN101022948B/en
Priority to CA2581040A priority patent/CA2581040C/en
Priority to PL05790749T priority patent/PL1827812T3/en
Priority to EP05790749.5A priority patent/EP1827812B1/en
Priority to JP2007533485A priority patent/JP5031571B2/en
Publication of WO2006036409A2 publication Critical patent/WO2006036409A2/en
Publication of WO2006036409A3 publication Critical patent/WO2006036409A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0052—Digital printing on surfaces other than ordinary paper by thermal printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2427/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers

Definitions

  • This invention relates to a process for forming an extruded article having a weatherable coating by the in-line spray, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or inkjet application of a polymeric solution onto an extruded thermoplastic substrate.
  • the preferred substrates for which the process are PVC and polyolefins.
  • the invention also relates to PVC and polyolefin articles coated by the process.
  • Polyvinyl chloride (PVC) and polyolefin (PO) are economical thermoplastics that can be extruded into many useful articles.
  • PVC and polyolefin articles discolor, lose gloss, become chalky in appearance and embrittle if exposed to sunlight for extended periods of time. The discoloration and embrittlement is especially detrimental for articles intended for long-term weather exposure, such as house siding, window frames, rain systems, soffits, trim, pipe, panels, etc.
  • Stabilizer systems such as lead stabilizers, calcium-zinc stabilizers, and the use of high levels of titanium dioxide pigment have be employed in the PVC resin.
  • An alternative method has been to employ a thin weatherable capstock over the PVC or PO substrate applied as a laminate or by co-extrusion.
  • the capstock may be stabilized PVC, or a non-PVC polymer. Acrylics have been favored as capstocks for their
  • US 5,972,514 describes a means of coating a PVC substrate with a polymer coating using an air or airless spray, or an electrostatic process. The coating is then crosslinked by
  • KYNAR polyvinylidene coatings are formed onto flexible PVC by means of lamination of a pre-printed, pre-coated or clear PVDF flexible film. There is a need for a better in-line method of forming a weatherable protective coating onto a rigid PVC or PO substrate.
  • a weatherable protective coating can be formed onto a PVC or polyolefin extruded substrate by the in-line application of a polymeric solution or suspension by means of inkjet, brush-coat, roll-coat, gravure printing, flexographic printing, thermal transfer printing or spray application.
  • a further advantage of inline coating application by any of these methods is that color designs are easily created and readily customized or adjusted or matched on the extruded PVC or polyolefin.
  • Another object of the invention is to provide a means of applying a colored pattern and a weatherable coating onto a PVC or polyolefin substrate.
  • a process for forming a weatherable PVC or PO article comprising inline spray-coat, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer print or inkjet application of a polymeric solution onto extruded PVC.
  • the present invention relates to an in-line process for the formation of a weatherable extruded article by spray— coat, roll-coat, brush-coat, gravure print,
  • the PVC substrate is rigid polyvinyl chloride.
  • the PVC may be any vinyl chloride polymer or copolymer composition, particularly one or more addition polymers chosen from the group formed by vinyl chloride homopolymers, which can optionally be overchlorinated, and the copolymers, optionally grafted, which result from the copolymerization of vinyl chloride with one or more ethylenically unsaturated
  • Comonomers useful in the formation of a PVC copolymer include, but are not limited to, vinylidene halides such as vinylidene chloride or fluoride, vinyl carboxylates, such as vinyl acetate, vinylpropionate or vinyl butyrate, acrylic and methacrylic acids, and the nitriles, amides and alkylesters which derive therefrom, especially acrylonitrile, acrylamide, methacrylamide, methylmethacrylate, methyl acrylate, butyl acrylate ethyl acrylate.
  • vinylidene halides such as vinylidene chloride or fluoride
  • vinyl carboxylates such as vinyl acetate, vinylpropionate or vinyl butyrate
  • acrylic and methacrylic acids and the nitriles, amides and alkylesters which derive therefrom, especially acrylonitrile, acrylamide, methacrylamide, methylmethacrylate, methyl acrylate, butyl acrylate e
  • 2-ethylhexyl acrylate vinyl aromatic derivatives, such as styrene or vinyl naphthalene, or olefins, such as bicycle[2.2.]hept-2-ene, ethylene, propene or 1-butene.
  • the generally preferred PVC polymers are the homo- and copolymers of vinyl chloride, having a K value of about 65.
  • Polyolefin substrates include useful in the invention include polyethylene, polypropylene, polybutylene, polyisoprene, their copolymers and mixtures thereof.
  • the polymeric solution for spray-coat, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer print or inkjet application to the PVC or PO extruded substrate is a pigmented or non-pigmented, dye-containing or dye-free solvent or aqueous solution, dispersion, emulsion, or combination thereof of from 2 to 50 percent solids by weight, and preferably from 10 to 50% solids by weight.
  • polymers useful in the solution, dispersion or emulsion used to form a coating on the PVC contain polymeric systems have weight average molecular weights greater than 100,000 and have glass transition temperatures of between -5O 0 C and +5O 0 C.
  • Polymers useful in the polymeric solution, dispersion or emulsion of the invention include, but are not limited to, acrylics, fluorinated polymers, urethanes, silicones, polysiloxanes, polyesters, epoxies, stabilized PVC and mixtures thereof in solution, dispersion or emulsion form.
  • the polymeric solution contains one
  • fluoropolymers which are known for their excellent weatherability. These may be homopolymers, such as polyvilidene fluoride, or copolymers and terpolymers, such as, but not limited to, vinylidene fluoride/ hexafluoropropylene copolymer, vinylidene fluoride/chlorotetrafluoroethylene copolymer, vinylidene fluoride/tetrafluoroethylene o copolymer ethylene/tetrafluoroethylene copolymer, fluorinated ethylene propylene (FEP)
  • FEP fluorinated ethylene propylene
  • Fluoropolymers of the invention also include partially fluorinated polymers, such as ETFE and ECTFE, which may have similar decomposition products as fully fluorinated polymers.
  • the fluoropolymer is a polyvinylidene fluoride polymer.
  • PVDF polyvinylidene fluoride polymer
  • PVDF resin or PVDF polymer refers not only to homopolymers of PVDF but also to copolymers prepared from at least about 75% by weight of vinylidene fluoride (VDF) monomer.
  • Comonomers may include other fluorinated monomers such as: vinyl fluoride, hexafluoropropylene (HFP), chlorotetrafluoroethylene (CTFE), tetrafluoroethylene (TFE),
  • PVDF coated PVC articles have improved gloss and color retention, as well as stain resistance.
  • the polymeric solution, dispersion, or emulsion for use in the application onto the PVC or polyolef ⁇ n is formed by dissolving or dispersing the polymer in a solvent or 5 aqueous media.
  • solvents include, but are not limited to, acetone, tetrahydrofuran, hexane, heptane, n-methyl pyrrolidone, methyl ethyl ketone, methyl acetate, ethyl acetate, cyclohexanone, isophorone, water, water with water-miscible solvents, and mixtures
  • the coatings are applied at viscosities of 0.1 to 5000 cps, and preferably from 1 - 500 cps, when measured at room temperature. Those viscosities may be appreciably lower at the actual application temperature which will typically be between 5O 0 C and 125 0 C.
  • additives known in art may also be added to the polymeric coating solution or suspension including, but not limited to: dyes, colorants, impact modifiers, antioxidants, flame-retardants, ultraviolet stabilizers, flow aids, metal additives for electronic magnetic radiation shielding, defoamers and anti-static agents.
  • the polymeric solution may be applied to the extruded PVC at any point in the in ⁇ line process at temperatures ranging from 5O 0 C to 125 0 C.
  • the inkjet, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or spray coating apparatus is placed immediately after the substrate extrusion, and before the embossing process.
  • the inkjet, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or spray apparatus is placed in-line after the embossing operation.
  • the coated PVC or polyoilefin substrate is generally cut, stamped and formed into a final article. Rigid PVC or polyolefin is especially useful for house siding, window frames, rain systems, soffits, trim, pipe, and panels.
  • the coating will be applied at a dry film thickness of 0.02 mils to 4.0 mils with a preferred range of 0.02 to 1.2 mils.
  • weatherable polymeric coating is generally applied only to one side of the PVC or polyolefin substrate, it is within the scope of the invention to apply the weatherable polymeric coating to both sides of the substrate.
  • the double side coated substrate could have both sides coated with the same or different polymeric solution during the same coating cycle at the same coating station or at different stations.
  • the present invention saves production costs by providing a very thin film of the more expensive weatherable polymer on an inexpensive rigid PVC or polyolefin substrate. It also allows for production flexibility, in that the in-line application can occur anywhere in the production process. By requiring only one extruder, higher throughput is possible without the need to match the differential cooling rates of 2 extruders (one being the substrate, the other being the capstock).
  • Another aspect of the invention is the ability to provide a virtually endless spectrum of colors in the weatherable coating, ranging from a clear coating to black, and all colors in the visible spectrum limited only by the colorimetric capabilities of the colorants. Darker colors are easily achieved, as the films are thin compared to the current technology, and heat is quickly dissipated. Additionally, rapid color-to-color changeover is possible by simply changing the polymeric coating solutions or the ratios of in-line blended colored coatings. This saves both time and off-spec material involved in current processes. The use of four-color process printing, coating would allow for in-situ color matching and digital adjustment. Custom colors would be easily achieved.
  • the ink-jet process would also allow for the printing of complex colored patterns such as faux-brick, faux stucco and other patterns onto the PVC or polyolefin substrate.
  • complex colored patterns such as faux-brick, faux stucco and other patterns onto the PVC or polyolefin substrate.
  • a rigid substrate is as endless as one's imagination.
  • a white coating is applied first to the rigid substrate, followed by the ink jetted coating.
  • the effect of the inkjetted pattern is better distinguished on a white background.
  • a white coating of an epoxy or PVDF is preferred.
  • the PVC or PO extruded substrate is
  • Example 1 coextruded with a capstock, followed by application of the weatherable coating.
  • PVDF coating mixture One would form a PVDF coating mixture by first making a 15% PVDF solution in Methyl Ethyl Ketone (solvent) and optionally adding colorant and/or additives. The PVDF coating is then placed into one or more reservoirs of an inkjet printer. The ink-jet printer is calibrated to print the precise pattern and polymer density onto PVC or polyolefin as it is extruded. The coated extruded PVC or polyolefin is then formed into a final article such as a sheet of vinyl siding, a window profile, a fence post, or other article.
  • a PVDF coating mixture is prepared by first making a solution of PVDF at 10% solids in Acetone and n-methyl pyrrolidone. Optionally, pigments, dyes, additives or co-resins are also incorporated. This coating is then spray applied to extruded PVC or polyolefin either before or after the embossing step. The coated extrudate is then cut into planks from which vinyl decking is made.
  • a white epoxy primer coating is applied inline to extruded PVC or polyolefin. It is subsequently overcoated by ink-jet process-printing a faux-brick design pattern. The coated PVC extrudate is then cut and shaped into vinyl siding panels.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

This invention relates to a process for forming a PVC article having a weatherable coating by the in-line spray, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or inkjet application of a polymeric solution onto extruded PVC as it is being extruded. The invention also relates to rigid PVC articles coated by the process. A polyvinylidene fluoride coating can be applied to PVC to form an article having improved gloss, good weatherability, good color retention and stain resistance.

Description

PROCESS FOR COATING EXTRUDED THERMOPLASTIC SUBSTRATES AND OBJECTS FORMED THEREBY
This application claims benefit under U. S. C. §119(e) of US provisional application 60/612,678, filed September 24, 2004.
FIELD OF THE INVENTION
This invention relates to a process for forming an extruded article having a weatherable coating by the in-line spray, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or inkjet application of a polymeric solution onto an extruded thermoplastic substrate. The preferred substrates for which the process are PVC and polyolefins. The invention also relates to PVC and polyolefin articles coated by the process.
BACKGROUND OF THE INVENTION
Polyvinyl chloride (PVC) and polyolefin (PO) are economical thermoplastics that can be extruded into many useful articles. Unfortunately, PVC and polyolefin articles discolor, lose gloss, become chalky in appearance and embrittle if exposed to sunlight for extended periods of time. The discoloration and embrittlement is especially detrimental for articles intended for long-term weather exposure, such as house siding, window frames, rain systems, soffits, trim, pipe, panels, etc. Many approaches have been used to improve the performance of the PVC and PO articles. Stabilizer systems such as lead stabilizers, calcium-zinc stabilizers, and the use of high levels of titanium dioxide pigment have be employed in the PVC resin.
An alternative method has been to employ a thin weatherable capstock over the PVC or PO substrate applied as a laminate or by co-extrusion. The capstock may be stabilized PVC, or a non-PVC polymer. Acrylics have been favored as capstocks for their
color stability in outdoor exposure, however they are higher in cost. Film laminates of polyvinylidene difluoride have also been used. Several patents which describe the use of weatherable laminates for rigid PVC substrate compositions include EP 1061100; EP 0473379; US 4,141,935; US 4,169,180; US 4,183,777, US 5,306,548; and US 5,976,671. The problem with capstock and laminate processes is that they require a second piece of extrusion or laminating equipment that the throughput rates must be matched to account for differential cooling. Additionally, there is a significant loss of time and material wastage when the production line switches from one color to another. A further difficulty arises in the production/fabrication of dark colored PVC or PO articles, as the slower heat dissipation from the formed article causes production issues as well as occasional failure in the field (delamination, embrittlement, color loss, gloss loss,
chalking).
US 5,972,514 describes a means of coating a PVC substrate with a polymer coating using an air or airless spray, or an electrostatic process. The coating is then crosslinked by
IR radiation.
InkJet printing onto non-absorbant plastic substrates, such as transparencies, is
known in the art, such as in US 5,555,006.
KYNAR polyvinylidene coatings are formed onto flexible PVC by means of lamination of a pre-printed, pre-coated or clear PVDF flexible film. There is a need for a better in-line method of forming a weatherable protective coating onto a rigid PVC or PO substrate.
Surprisingly it has been found that a weatherable protective coating can be formed onto a PVC or polyolefin extruded substrate by the in-line application of a polymeric solution or suspension by means of inkjet, brush-coat, roll-coat, gravure printing, flexographic printing, thermal transfer printing or spray application. A further advantage of inline coating application by any of these methods is that color designs are easily created and readily customized or adjusted or matched on the extruded PVC or polyolefin.
SUMMARY OF THE INVENTION It is an object of the invention to provide an in-line process for applying a weatherable coating onto an extruded substrate such as PVC or a polyolefin.
It is a further object of the invention to provide a method for printing designs onto a PVC or polyolefin substrate and a protective coating in a one-step process.
Another object of the invention is to provide a means of applying a colored pattern and a weatherable coating onto a PVC or polyolefin substrate.
The objectives of the invention are achieved, in accordance with the principles of a preferred embodiment of the invention, by a process for forming a weatherable PVC or PO article comprising inline spray-coat, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer print or inkjet application of a polymeric solution onto extruded PVC.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to an in-line process for the formation of a weatherable extruded article by spray— coat, roll-coat, brush-coat, gravure print,
flexographic print, thermal transfer print or inkjet application of a polymeric solution. PVC and polyolefin articles are preferred. The PVC substrate is rigid polyvinyl chloride. The PVC may be any vinyl chloride polymer or copolymer composition, particularly one or more addition polymers chosen from the group formed by vinyl chloride homopolymers, which can optionally be overchlorinated, and the copolymers, optionally grafted, which result from the copolymerization of vinyl chloride with one or more ethylenically unsaturated
comonomers.
Comonomers useful in the formation of a PVC copolymer include, but are not limited to, vinylidene halides such as vinylidene chloride or fluoride, vinyl carboxylates, such as vinyl acetate, vinylpropionate or vinyl butyrate, acrylic and methacrylic acids, and the nitriles, amides and alkylesters which derive therefrom, especially acrylonitrile, acrylamide, methacrylamide, methylmethacrylate, methyl acrylate, butyl acrylate ethyl acrylate. Or 2-ethylhexyl acrylate, vinyl aromatic derivatives, such as styrene or vinyl naphthalene, or olefins, such as bicycle[2.2.]hept-2-ene, ethylene, propene or 1-butene.
The generally preferred PVC polymers are the homo- and copolymers of vinyl chloride, having a K value of about 65.
Polyolefin substrates include useful in the invention include polyethylene, polypropylene, polybutylene, polyisoprene, their copolymers and mixtures thereof.
The polymeric solution for spray-coat, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer print or inkjet application to the PVC or PO extruded substrate is a pigmented or non-pigmented, dye-containing or dye-free solvent or aqueous solution, dispersion, emulsion, or combination thereof of from 2 to 50 percent solids by weight, and preferably from 10 to 50% solids by weight.
The polymers useful in the solution, dispersion or emulsion used to form a coating on the PVC contain polymeric systems have weight average molecular weights greater than 100,000 and have glass transition temperatures of between -5O0C and +5O0C. Polymers useful in the polymeric solution, dispersion or emulsion of the invention include, but are not limited to, acrylics, fluorinated polymers, urethanes, silicones, polysiloxanes, polyesters, epoxies, stabilized PVC and mixtures thereof in solution, dispersion or emulsion form.
5 In one preferred embodiment of the invention, the polymeric solution contains one
or more fluoropolymers which are known for their excellent weatherability. These may be homopolymers, such as polyvilidene fluoride, or copolymers and terpolymers, such as, but not limited to, vinylidene fluoride/ hexafluoropropylene copolymer, vinylidene fluoride/chlorotetrafluoroethylene copolymer, vinylidene fluoride/tetrafluoroethylene o copolymer ethylene/tetrafluoroethylene copolymer, fluorinated ethylene propylene (FEP)
and mixtures thereof. Fluoropolymers of the invention also include partially fluorinated polymers, such as ETFE and ECTFE, which may have similar decomposition products as fully fluorinated polymers.
Preferably the fluoropolymer is a polyvinylidene fluoride polymer. "PVDF" or 5 PVDF resin or PVDF polymer refers not only to homopolymers of PVDF but also to copolymers prepared from at least about 75% by weight of vinylidene fluoride (VDF) monomer. Comonomers may include other fluorinated monomers such as: vinyl fluoride, hexafluoropropylene (HFP), chlorotetrafluoroethylene (CTFE), tetrafluoroethylene (TFE),
and vinyl fluoride. Preferred are the homopolymers and the copolymers prepared from o VDF and HFP to which small amounts (up to about 5 weight percent, preferably about 0.01 to about 0.05 weight percent) of PTFE may be added. PVDF coated PVC articles have improved gloss and color retention, as well as stain resistance.
The polymeric solution, dispersion, or emulsion for use in the application onto the PVC or polyolefϊn is formed by dissolving or dispersing the polymer in a solvent or 5 aqueous media. Useful solvents include, but are not limited to, acetone, tetrahydrofuran, hexane, heptane, n-methyl pyrrolidone, methyl ethyl ketone, methyl acetate, ethyl acetate, cyclohexanone, isophorone, water, water with water-miscible solvents, and mixtures
thereof. The coatings are applied at viscosities of 0.1 to 5000 cps, and preferably from 1 - 500 cps, when measured at room temperature. Those viscosities may be appreciably lower at the actual application temperature which will typically be between 5O0C and 1250C.
Other additives known in art may also be added to the polymeric coating solution or suspension including, but not limited to: dyes, colorants, impact modifiers, antioxidants, flame-retardants, ultraviolet stabilizers, flow aids, metal additives for electronic magnetic radiation shielding, defoamers and anti-static agents. The polymeric solution may be applied to the extruded PVC at any point in the in¬ line process at temperatures ranging from 5O0C to 1250C.
In one embodiment of the invention, the inkjet, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or spray coating apparatus is placed immediately after the substrate extrusion, and before the embossing process. In another embodiment of the invention the inkjet, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or spray apparatus is placed in-line after the embossing operation. Following the embossing step, the coated PVC or polyoilefin substrate is generally cut, stamped and formed into a final article. Rigid PVC or polyolefin is especially useful for house siding, window frames, rain systems, soffits, trim, pipe, and panels. The coating will be applied at a dry film thickness of 0.02 mils to 4.0 mils with a preferred range of 0.02 to 1.2 mils.
While the weatherable polymeric coating is generally applied only to one side of the PVC or polyolefin substrate, it is within the scope of the invention to apply the weatherable polymeric coating to both sides of the substrate. The double side coated substrate could have both sides coated with the same or different polymeric solution during the same coating cycle at the same coating station or at different stations. The present invention saves production costs by providing a very thin film of the more expensive weatherable polymer on an inexpensive rigid PVC or polyolefin substrate. It also allows for production flexibility, in that the in-line application can occur anywhere in the production process. By requiring only one extruder, higher throughput is possible without the need to match the differential cooling rates of 2 extruders (one being the substrate, the other being the capstock).
Another aspect of the invention is the ability to provide a virtually endless spectrum of colors in the weatherable coating, ranging from a clear coating to black, and all colors in the visible spectrum limited only by the colorimetric capabilities of the colorants. Darker colors are easily achieved, as the films are thin compared to the current technology, and heat is quickly dissipated. Additionally, rapid color-to-color changeover is possible by simply changing the polymeric coating solutions or the ratios of in-line blended colored coatings. This saves both time and off-spec material involved in current processes. The use of four-color process printing, coating would allow for in-situ color matching and digital adjustment. Custom colors would be easily achieved.
The ink-jet process would also allow for the printing of complex colored patterns such as faux-brick, faux stucco and other patterns onto the PVC or polyolefin substrate. With digital computer control, the range of possible patterns for applying to the exterior of
a rigid substrate is as endless as one's imagination. In one embodiment, a white coating is applied first to the rigid substrate, followed by the ink jetted coating. The effect of the inkjetted pattern is better distinguished on a white background. A white coating of an epoxy or PVDF is preferred.
In still another embodiment of the invention, the PVC or PO extruded substrate is
coextruded with a capstock, followed by application of the weatherable coating. Examples Example 1 :
One would form a PVDF coating mixture by first making a 15% PVDF solution in Methyl Ethyl Ketone (solvent) and optionally adding colorant and/or additives. The PVDF coating is then placed into one or more reservoirs of an inkjet printer. The ink-jet printer is calibrated to print the precise pattern and polymer density onto PVC or polyolefin as it is extruded. The coated extruded PVC or polyolefin is then formed into a final article such as a sheet of vinyl siding, a window profile, a fence post, or other article.
Example 2:
A PVDF coating mixture is prepared by first making a solution of PVDF at 10% solids in Acetone and n-methyl pyrrolidone. Optionally, pigments, dyes, additives or co-resins are also incorporated. This coating is then spray applied to extruded PVC or polyolefin either before or after the embossing step. The coated extrudate is then cut into planks from which vinyl decking is made.
Example 3 :
A white epoxy primer coating is applied inline to extruded PVC or polyolefin. It is subsequently overcoated by ink-jet process-printing a faux-brick design pattern. The coated PVC extrudate is then cut and shaped into vinyl siding panels.

Claims

What is claimed is:
I . A process for forming a weatherable polyvinyl chloride (PVC) or polyolefin (PO) article comprising applying a polymeric solution in-line onto extruded PVC or PO to form a weatherable coating.
2. The process of claim 1 wherein the polymeric solution is applied by inline spray, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat, or inkjet application.
3. The process of claim 1 wherein said polymeric solution is colorant-containing or clear.
4. The process of claim 1 wherein said polymeric solution is a solvent-based solution or dispersion.
5. The process of claim 1 wherein said polymeric solution is an aqueous-based solution, dispersion or emulsion.
6. The process of claim 1 wherein the polymeric solution comprises a fluorinated polymer, an acrylic polymer, a polyurethane polymer, or a polyester.
7. The process of claim 1 wherein said fluorinated polymer comprises a polyvinylidene homopolymer or co-polymer.
8. The process of claim 1 wherein said weatherable polymeric coating is 0.02 to 4.0 mils thick, based on dry film thickness.
9. The process of claim 8 wherein said weatherable polymeric coating is 0.02 to 1.2
mils thick, based on dry film thickness.
10. The process of claim 1 further comprising the step of covering the PVC or PO substrate with a capstock or coating, prior to application of the weatherable coating.
I I. An extruded PVC or PO article comprising a PVC or PO substrate having a weatherable polymeric coating that has been applied by inkjet, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or by a spray process.
12. The extruded PVC or PO article of claim 11 wherein said weatherable polymeric coating has a design formed by two or more different colored inkjet pixels.
PCT/US2005/030320 2004-09-24 2005-08-26 Process for coating extruded thermoplastic substrates and objects formed thereby Ceased WO2006036409A2 (en)

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CN2005800313819A CN101022948B (en) 2004-09-24 2005-08-26 Coating method for extruded thermoplastic substrates and objects formed therefrom
CA2581040A CA2581040C (en) 2004-09-24 2005-08-26 Process for coating extruded thermoplastic substrates and objects formed thereby
PL05790749T PL1827812T3 (en) 2004-09-24 2005-08-26 Process for coating extruded thermoplastic substrates and objects formed thereby
EP05790749.5A EP1827812B1 (en) 2004-09-24 2005-08-26 Process for coating extruded thermoplastic substrates and objects formed thereby
JP2007533485A JP5031571B2 (en) 2004-09-24 2005-08-26 Method for coating extruded thermoplastic substrates and articles formed thereby

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US60/612,678 2004-09-24
US11/192,204 2005-07-28
US11/192,204 US8071176B2 (en) 2004-09-24 2005-07-28 Process for forming a weatherable polyvinyl chloride or polyolefin article

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WO2006036409A3 (en) 2006-11-09
JP5031571B2 (en) 2012-09-19
KR101269495B1 (en) 2013-05-31
KR20070072496A (en) 2007-07-04
CA2581040A1 (en) 2006-04-06
PL1827812T3 (en) 2019-04-30
CA2581040C (en) 2013-01-15
EP1827812B1 (en) 2018-10-10
CN101022948A (en) 2007-08-22
US8071176B2 (en) 2011-12-06
US20060068131A1 (en) 2006-03-30
EP1827812A2 (en) 2007-09-05
EP1827812A4 (en) 2010-07-21
CN101022948B (en) 2011-08-24
JP2008514403A (en) 2008-05-08

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