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WO1999007787A1 - Procede et composition pour l'amelioration de la peignabilite de polyolefines - Google Patents

Procede et composition pour l'amelioration de la peignabilite de polyolefines Download PDF

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Publication number
WO1999007787A1
WO1999007787A1 PCT/IL1998/000367 IL9800367W WO9907787A1 WO 1999007787 A1 WO1999007787 A1 WO 1999007787A1 IL 9800367 W IL9800367 W IL 9800367W WO 9907787 A1 WO9907787 A1 WO 9907787A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic polyolefin
composition
parts
weight
polyolefinic
Prior art date
Application number
PCT/IL1998/000367
Other languages
English (en)
Inventor
Susan Agro
Jose D. Reyes
Original Assignee
Bromine Compounds Ltd.
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 Bromine Compounds Ltd. filed Critical Bromine Compounds Ltd.
Priority to EP98936658A priority Critical patent/EP0931108A1/fr
Publication of WO1999007787A1 publication Critical patent/WO1999007787A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • This invention relates to a process for improving the adhesion of paints to plastic compositions based on thermoplastic polyolefin polymers and copolymers such as polypropylene, propylene-ethylene copolymers and the like. It also relates to compositions based on said polymers and copolymers and having improved paintability, to a process for making painted pieces and parts of any kind based on said compositions, as well as to the resulting painted pieces and parts.
  • polyolefin substrates In the present art, the automotive industry uses polyolefin substrates and paints them with solvent-based paint systems comprising a primer layer, a urethane-base coat or pigment coat and a clear urethane top coat.
  • An example of such polyolefin substrates to which this invention particularly, but not exclusively, relates is a thermoplastic polyolefin (sometimes briefly indicated as TPO) containing 87-88% of propylene units and 12-13% of ethylene units.
  • TPO thermoplastic polyolefin
  • the painting process presently used is complex and costly.
  • a typical painting system comprises, e.g., three or four painting booths for priming, applying a base coat in one or two operations and applying the final clear coat. Baking of the primer and at least of the final coat is of course required. The cost of painting is estimated to bet 50% or more of then total cost of the painted component.
  • thermoplastic polyolefins It is a purpose of this invention to achieve an improvement on prior art systems in the art of painting thermoplastic polyolefins.
  • thermoplastic polyolefin composition to which paints strongly adhere without the need of a primer.
  • the invention provides a process for improving the adhesion of paints or dyes to thermoplastic polyolefin (TPO) substrates, in particular polypropylene and ethylene-propylene rubber (EPR or EPDM) as defined in "Plastics and Materials", J.A. Brydsin - 6th edition - British Plastics and Rubber pp. 291-292 and 856, and the like, which comprises the step of mixing and/or compounding with the TPO: a) an unsubstituted or brominated epoxy resin having the formula
  • each of the X's can be, independently of the others, H or Br, which has a molecular weight of at least 340 if all X's are H and of at least 656 if all X's are Br, n being in average between 0 and 150; and b) preferably, a polyolefinic modifier, which is a reactive polyolefin containing carboxylic acid functionality, in particular a maleated polyolefin.
  • polyolefinic modifiers are known in the art and used to improve the mechanical properties of polyolefins. They are sometimes called “modified” olefin polymers or copolymers. Therefore, for the sake of clarity, it is specified that the expression “polyolefinic modifiers” and “modified polyolefins”, when used in this specification and claims, will have the same meaning.
  • the thermoplastic polyolefin substrates, compounded with the aforesaid epoxy oligomers and, optionally, with the said polyolefinic modifiers, according to the invention will be called “compounded polyolefins" or "compounded TPO".
  • An example of maleated polyolefin resin usable according to the invention is that manufactured and sold by Uniroyal under the trade name Uniroyal
  • Polybond 3150 Said maleated propylene resin has approximately 0.6% maleic acid functionality.
  • Other modified polyolefin resins can be used according to the invention: for instance, acryhc acid functional polyethylenes or polypropylenes (having approximately 0.1-6% by weight of carboxylic groups).
  • the compounding can be carried out in known ways, e.g. by extruding the components together in one or more passes.
  • the extrudates can then be pelletized and molded or otherwise processed to produce the desired pieces or parts.
  • the invention also provides a composition of matter which comprises: a) a thermoplastic polyolefin (TPO) such as polypropylene, propylene-ethylene copolymers and the like; b) an epoxy resin having the formula set forth above; and, preferably, c) a polyolefinic modifier, as hereinbefore defined.
  • TPO thermoplastic polyolefin
  • an epoxy resin having the formula set forth above
  • a polyolefinic modifier as hereinbefore defined.
  • Such a composition of matter can be painted by known techniques, without the application of a primer. Therefore the invention also includes a process for making painted pieces and parts, in particular automobile bumpers and other parts, by compounding a TPO with an epoxy resin, as hereinbefore defined, and preferably, a polyolefinic modifier, making the part to be painted by known methods from the compounded TPO, and painting it without the application of a primer.
  • the invention also includes the painted pieces or parts made by this process.
  • Other thermoplastic polyolefines besides those mentioned so far, may be chosen from polyethylene (low density polyethylene, hnear low density polyethylene, high density polyethylene), block or random copolymers of polyethylene and polypropylene, including ethylene-propylene rubbers and alike.
  • plastics additives or modifiers such as e.g. antioxidants, lubricants, UV/light stabilizers, pigments, flame retardants, antimony trioxide, fillers, foaming agents, glass fiber reinforcement etc.
  • a TPO was used containing 87-88% of propylene units and 12-13% of ethylene units.
  • the said TPO was compounded with a maleated polyolefin and an epoxy resin.
  • the compounding was executed using a Brabender 42mm, counter-rotating, intermeshing twin-screw extruder, carrying out two passes through the extruder and with temperature profiles that were temperatures compatible with the components compounded into the TPO and which were in general approximately 195-200°C.
  • the extruder was operated at 90 rpm and 3-5 Amps.
  • the compounded TPO extrudates were pelletized.
  • the pellets were compression molded as 1/8" plaques or plates using a heated hydraulic press.
  • Specimen plaques were prepared by molding the pellets between 1/8" thick aluminum plates with a Mylar release film at a temperature of about 390°F.
  • the pellets and the molding plates were preheated in the heated press for 4 minutes before pressing for 2 minutes using 300 psi pressure and cooling in a 55°F press for 2 minutes.
  • the compression molded plaques were cleaned with methanol prior to painting.
  • the control plaques not prepared according to the invention, viz.
  • Uniroyal Polybond 3150 was used as the modified (maleated) polypropylene resin.
  • epoxy resins having the formula set forth above, were used brominated epoxy resins having the formula set forth hereinbefore, wherein all X's are bromine, manufactured and sold by Dead Sea Bromine Group, under the collective trade designation F-2000.
  • F-2000 brominated epoxy resins having the formula set forth hereinbefore, wherein all X's are bromine, manufactured and sold by Dead Sea Bromine Group, under the collective trade designation F-2000.
  • F-2200HM which contains 48% bromine and has a molecular weight of about 700, gave excellent results, but the other brominated epoxy resins of said series, e.g. those designated as F-2016 and F-2400E, which have higher molecular weights than F-2200HM - 1,600 and 30,000 respectively - gave substantially the same results, when used in the same amounts with the polyolefinic modifier.
  • a urethane base coat specifically constituted by Red Spot 317LE21600V Cream White 2K Urethane Base Coat EA16935 was applied and was then air-dried at ambient conditions for 5 minutes followed by a 30 minute post-cure at 170°F. Said base coat was then over-coated with a urethane paint, specifically Red Spot 317LE, with the addition of a catalyst having the trade designation LE9426F. A first set of over-coated samples were dried at ambient conditions for 5 minutes, followed by a 30 minute bake at 170°F. Another set, similarly base-coated and top-coated, were air-dried for 5 minutes but cured at 250°F for 30 minutes.
  • the painted and cured panels were allowed to condition for 72 hours prior to testing.
  • the adhesion of the paint to the TPO was evaluated using the ASTM D3359 Standard Test Method for Measuring Adhesion by Tape Test - Method A (X-Cut). Those specimens that demonstrated good adhesion by said method were then tested by Method B (Lattice Pattern).
  • the aforesaid Method A entailed making an X-shaped cut through the coating to the substrate, applying pressure-sensitive tape over the cut and then removing it.
  • the adhesion of the coating was assessed qualitatively on a scale from 0A to 5A, 5A meaning 100% adhesion, 0A meaning no adhesion.
  • Method B entailed cutting a grid of 6x6 slices spread 1 mm apart through the coating to the substrate. A piece of tape was applied over the grid and was then peeled rapidly away at an angle of 180°. The amount of paint that was moved was evaluated qualitatively on a scale of 0B to 5B, 5B meaning 100% adhesion and 0B meaning no adhesion.
  • the attached Table I illustrates eleven different substrate formulations.
  • one of them contains a PEA commercially known as Jeffamine M-2070, which is a polyoxyalkyleneamine containing primary amino groups attached to the terminals of a polyether backbone and has a molecular weight of about 2000.
  • the Jeffamines are produced by Huntsman Corporation and are considered a good reference in industry.
  • epoxy resins the formulations of the Examples contain those designated as F-2200HM, F-2016 and F-2400E.
  • the amounts of components in Table I are indicated as percentages by weight.
  • Table II shows the results obtained by applying Methods A and B, described above, to the various specimens.
  • Table II Adhesion properties.
  • the process of this invention can be applied to improve the dyeability of polypropylene fibers and textile products, and the compositions of matter according to the invention can be in the form of fibers and textile products.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé pour améliorer l'adhérence de peintures et de pigments sur des substrats en polyoléfines thermoplastiques. Ledit procédé consiste à mélanger une base de polyoléfine thermoplastique et une résine époxy de formule (1) et/ou à composer un mélange à partir de ces dernières. Dans ladite formule (1), chaque X' représente séparément hydrogène ou brome, et n vaut en moyenne 0 à 150.
PCT/IL1998/000367 1997-08-07 1998-08-06 Procede et composition pour l'amelioration de la peignabilite de polyolefines WO1999007787A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98936658A EP0931108A1 (fr) 1997-08-07 1998-08-06 Procede et composition pour l'amelioration de la peignabilite de polyolefines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL121491 1997-08-07
IL12149197A IL121491A0 (en) 1997-08-07 1997-08-07 Process and composition for improving the paintability of polyolefins

Publications (1)

Publication Number Publication Date
WO1999007787A1 true WO1999007787A1 (fr) 1999-02-18

Family

ID=11070476

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IL1998/000367 WO1999007787A1 (fr) 1997-08-07 1998-08-06 Procede et composition pour l'amelioration de la peignabilite de polyolefines

Country Status (3)

Country Link
EP (1) EP0931108A1 (fr)
IL (1) IL121491A0 (fr)
WO (1) WO1999007787A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011077439A1 (fr) 2009-12-24 2011-06-30 Bromine Compounds Ltd. Compositions ignifugées
WO2012127463A1 (fr) 2011-03-20 2012-09-27 Bromine Compounds Ltd. Composition retardatrice de flamme et polypropylène à haute résistance au choc, à retard de flamme

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4542164A (en) * 1982-10-04 1985-09-17 Toray Industries, Incorporated Flame-retardant polyolefin foam
US5198497A (en) * 1991-12-30 1993-03-30 Eastman Kodak Company Polyolefin, rubber and eva-maleic anhydride terpolymer blend
WO1997011122A1 (fr) * 1995-09-20 1997-03-27 Minnesota Mining And Manufacturing Company Reseaux polymeres de semi-interpenetration de resines epoxy et polyolefines, procedes de fabrication et d'utilisation associes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4542164A (en) * 1982-10-04 1985-09-17 Toray Industries, Incorporated Flame-retardant polyolefin foam
US5198497A (en) * 1991-12-30 1993-03-30 Eastman Kodak Company Polyolefin, rubber and eva-maleic anhydride terpolymer blend
WO1997011122A1 (fr) * 1995-09-20 1997-03-27 Minnesota Mining And Manufacturing Company Reseaux polymeres de semi-interpenetration de resines epoxy et polyolefines, procedes de fabrication et d'utilisation associes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011077439A1 (fr) 2009-12-24 2011-06-30 Bromine Compounds Ltd. Compositions ignifugées
US8991321B2 (en) 2009-12-24 2015-03-31 Bromine Compounds Ltd. Flame retarded compositions
WO2012127463A1 (fr) 2011-03-20 2012-09-27 Bromine Compounds Ltd. Composition retardatrice de flamme et polypropylène à haute résistance au choc, à retard de flamme

Also Published As

Publication number Publication date
EP0931108A1 (fr) 1999-07-28
IL121491A0 (en) 1998-02-08

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