WO2000027936A1 - Compositions de revetement contenant des interpolymeres aromatiques d'alpha-olefine/vinyle ou vinylidene et/ou des interpolymeres aliphatiques ou cycloaliphatiques de vinyle ou de vinylidene steriquement encombres - Google Patents

Compositions de revetement contenant des interpolymeres aromatiques d'alpha-olefine/vinyle ou vinylidene et/ou des interpolymeres aliphatiques ou cycloaliphatiques de vinyle ou de vinylidene steriquement encombres Download PDF

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Publication number
WO2000027936A1
WO2000027936A1 PCT/US1999/025826 US9925826W WO0027936A1 WO 2000027936 A1 WO2000027936 A1 WO 2000027936A1 US 9925826 W US9925826 W US 9925826W WO 0027936 A1 WO0027936 A1 WO 0027936A1
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WIPO (PCT)
Prior art keywords
styrene
vinyl
ethylene
percent
vinylidene
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PCT/US1999/025826
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English (en)
Inventor
Stephen M. Hoenig
Thomas P. Schuman
Malcolm F. Finlayson
William L. Dechent
Shelby F. Thames
Oliver W. Smith
John O. Bieser
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The Dow Chemical Company
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Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to AU17117/00A priority Critical patent/AU1711700A/en
Priority to JP2000581106A priority patent/JP2002529573A/ja
Publication of WO2000027936A1 publication Critical patent/WO2000027936A1/fr

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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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09D125/00—Coating compositions based on 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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0838—Copolymers of ethene with aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene

Definitions

  • This invention describes the use of substantially random interpolymers such as the ethylene-styrene interpolymers (ESI) as a component in coatings such as paints and inks for substrates such as ESI, polyethylene, polystyrene, acrylonitrile/butadiene/styrene, polypropylene, other olefinic and styrenic substrates; as well as non-plastic substrates including wood, metal, paper and cement.
  • ESI ethylene-styrene interpolymers
  • a coating such as a paint or ink
  • it has good adhesion to the substrate.
  • Another attribute of such a coating is that it be able to hold high concentrations of filler or pigments for subsequent delivery to the substrate surface.
  • a good coating should also allow control of the abrasion resistance, gloss, hardness, scratch resistance, low temperature flexibility, surface texture and filler holding capacity of the resulting coated surface.
  • adhesion occurs through chemical bonding or mechanical interlocking of the coating and the substrate.
  • mechanical interlocking good swelling of the substrate by a coating solvent is generally a prerequisite of the interlocking mechanism.
  • chemical bonding the presence of a solvent for the coating is not a prerequisite, but can be advantageous.
  • Injection molded articles such as toys, often require coatings for aesthetics.
  • toys are typically prepared either from styrenic polymers such as polystyrene, high impact polystyrene (HIPS), acrylonitrile/butadiene/styrene (ABS) or poly vinyl chloride (PVC) polymers (in the case of hard and stiff toys), or flexible poly vinyl chloride (f PVC) in the case of soft flexible toys.
  • HIPS high impact polystyrene
  • ABS acrylonitrile/butadiene/styrene
  • PVC poly vinyl chloride
  • f PVC flexible poly vinyl chloride
  • any multi-component toy having both hard and flexible parts must comprise f PVC and the more expensive ABS versus the less expensive f PVC PS combination.
  • a typical coating formulation would comprise an aromatic solvent (for example toluene, xylene, or ethylbenzene) with a styrenic block copolymer resin (for example SBS, SIS or SEBS).
  • aromatic solvent for example toluene, xylene, or ethylbenzene
  • styrenic block copolymer resin for example SBS, SIS or SEBS.
  • thermoplastic substrate combinations including polyolefms
  • pre-treatments include flame or corona-treatment (to oxidize the surface), or pre-coating with a primer to promote adhesion of the final coating.
  • coatings that have resin components which comprise one or more substantially random interpolymers which in turn comprise polymer units derived from ethylene and/or one or more ⁇ -olefin monomers with one or more vinyl or vinylidene aromatic monomers and/or aliphatic or cycloaliphatic vinyl or vinylidene monomers.
  • the substantially random interpolymer can be the major resin component of the formulation or can be present as a minor resin component for example when being used as an adhesion promoter.
  • the coatings of the present invention can further comprise an additional resin selected from the group consisting of styrenic homopolymers or copolymers, ethylene and/or ⁇ -olefin homopolymers or interpolymers, thermoplastic polyolefms (TPOs), engineering thermoplastics, styrenic block copolymers, elastomers, and the vinyl or vinylidene halide homopolymers and copolymers.
  • TPOs thermoplastic polyolefms
  • engineering thermoplastics styrenic block copolymers
  • elastomers elastomers
  • vinyl or vinylidene halide homopolymers and copolymers ethylene and/or ⁇ -olefin homopolymers or interpolymers.
  • the coatings of the present invention can further comprise a solvent system and one or more other additives including, but not limited to binders, surfactants, thinners, adhesion promoters, fillers, tackifiers and processing aids, antistatic agents hardening resins, surface modifying additives, and combinations thereof.
  • additives including, but not limited to binders, surfactants, thinners, adhesion promoters, fillers, tackifiers and processing aids, antistatic agents hardening resins, surface modifying additives, and combinations thereof.
  • the substantially random interpolymers may also be used as an additive in existing solvent borne coating formulations functioning as an adhesion promoter to low surface energy plastic substrates, such as ethylene-styrene copolymers or polyethylene, polystyrene, polypropylene, ABS, and other olefinic and styrenic substrates.
  • coatings for substrates comprising substantially random ethylene-styrene interpolymers substrates exhibit enhanced adhesive properties if said coatings comprise styrenic polymers including, but not limited to, styrene-butadiene-styrene (SBS), styrene- isoprene-styrene (SIS), styrene-ethylene-butylene-styrene (SEBS), or styrene-ethylene- propylene (SEP) block copolymers, aromatic solvents and optionally an adhesion enhancing additive, such as one or more substantially random ethylene/styrene interpolymer.
  • SBS styrene-butadiene-styrene
  • SIS styrene- isoprene-styrene
  • SEBS styrene-ethylene-butylene-styrene
  • SEP styrene-ethylene- propylene
  • the filler holding capacity of the substantially random interpolymers can be used to create a new, simplified paint or ink manufacturing process.
  • colors are first added to the substantially random interpolymer (via compounding or other melt mixing techniques) and then the resulting pigment containing compound is added directly to the let down solution.
  • This process represent a simplification over the more traditional paint or ink manufacturing processes which add the pigment via a mill base step.
  • any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, and time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • hydrocarbyl as employed herein means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or aliphatic substituted cycloaliphatic groups.
  • hydrocarbyloxy means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached.
  • interpolymer is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc.
  • dip is used herein to indicate that an excess coating of the coating formulations of the present invention runs off after removing from coating solution to give proper film thickness with an application viscosity intermediate between spray and brush (2 to 30 Poise), but formulated with 30 percent more volatile solvents content versus high boiling solvents in less viscous formulations (compared to brushing). Solvent volatility controls drip (set up) time and thus film thickness.
  • ball jar or ball mill (usually ceramic) is used herein to indicate ajar filled with grinding media and millbase to be ground into a fine dispersion. Grinding media is usually solid ceramic cylinders.
  • binder is used herein to indicate the non-volatile portion of the liquid vehicle of a coating. It encompasses all polymer components of a coating formulation and functions to bind or cement the pigment particles together, and the coating film as a whole, to the material to which it is applied.
  • coating is used herein to indicate a clear or opaque surface coverage, which can be either water- or organic solvent-based and includes paints, inks, powder and architectural coatings.
  • CPVC critical pigment volume concentration
  • crystalline is used herein to indicate the local or bulk material ordered molecular arrangement, the repeating pattern of which defines the crystal unit cell.
  • the entropic ordering of a crystal corresponds to a material heat of transition (that occurs usually below melt, above glass transition temperature) and can be onset by thermal anneal (for example, during processing) in materials prone to crystalline ordering.
  • dispenser is used herein to indicate an additive that increases the stability of a suspension of powders in a liquid medium.
  • dispersing resin is used herein to indicate the, generally, higher molecular weight (polymeric) dispersant that has many pigment affinic sites along the polymeric chain, which bridge the surface tensions between the pigment and resin, and solvent.
  • glass transition temperature is used herein to indicate the temperature at which molecular motion (flow) of a material's amorphous regions begins, with the material becoming fluid-like.
  • gloss is used herein to indicate the qualitative tactile test of touch sensation in comparison to kid-goatskin leather surface.
  • Hegman gauge is used herein to indicate a device to measure the fineness of dispersion of a pigment based on drawing a paint down with a steel blade over a channel machined in a stainless steel block of tapered depth and observing the minimum depth at which pigment particles are observed to interfere with the smooth wet surface of the paint.
  • letdown is used herein to indicate the process of paint manufacturing in which the pigment paste (mill base) is reduced (let down) by the addition of the remaining ingredients of the formula.
  • the definition is modified so that the correct application viscosity is obtained.
  • Application viscosity is dependent on the method of application; spray, brush, or dip. Each method implies a shear rate range. Shear rate is important for materials that become less viscous under shear (pseudoplastic or thixotropic flow).
  • leveling is used herein to indicate the measure of the ability of a wet coating to flow out to a smooth dry film after application so as to obliterate any surface irregularities, such as brush marks, roller marks, orange peel from spraying, peaks or craters which have been produced by the mechanical process of applying the film.
  • melt temperature is used herein to indicate the transition of bulk material to a fluid state
  • millbase is used herein to indicate the portion of the coating formulation which is charged into the dispersion mill or appartus, and usually consists of pigments, dispersant(s), solvent(s), surface (processing) additives such as antifoaming agents, and possibly binder resin(s).
  • PVC pigment volume concentration
  • vehicle is used herein to indicate the liquid portion of a coating in which the pigment is dispersed. It is composed of binder and thinner.
  • substrate as used herein to indicate the material of construction of an article which comprises any surface to be coated and includes, but is not limited to, the various plastics and polymers, metals, wood, paper, glass, cement and masonry.
  • article is used herein to indicate any structure prepared from a substrate which can be coated by a coating composition. These includes, but are not limited to, injection molded toys, durable goods, foams, films, sheets, fibers, injection molded, blow molded and calendered articles, flooring, wall coverings, decorative coatings and overlays.
  • melt blending process is used herein to indicate any mixing process in which one or more of the components to be mixed is in a molten state, and which processes include, but are not limited to, single and twin screw extrusion, Banbury mixing, Haake blending, calendering, melt milling and other thermoplastic processing operations.
  • substantially random in the substantially random interpolymer comprising polymer units derived from ethylene and/or one or more ⁇ -olefin monomers with one or more vinyl or vinylidene aromatic monomers and/or aliphatic or cycloaliphatic vinyl or vinylidene monomers
  • substantially random means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in POLYMER SEOUENCE DETERMINATION. Carbon- 1 NMR Method. Academic Press New York, 1977, pp. 71-78.
  • substantially random interpolymers do not contain more than 15 percent of the total amount of vinyl aromatic monomer in blocks of more than 3 units. This means that in the carbon "13 NMR spectrum of the substantially random interpolymer, the peak areas corresponding to the main chain methylene and methine carbons, representing either meso diad sequences or racemic diad sequences, should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.
  • the coatings of the present invention comprise (A) one or more substantially random interpolymers.
  • the substantially random interpolymer can be the major resin component of the coating formulation or can be present as a minor resin component, for example when being used as an adhesion promoter, or to impart specific enhancements to coating performance.
  • the coatings of the present invention can further comprise (B) one or more additional resin components selected from the group consisting of styrenic homopolymers or copolymers. ethylene and/or ⁇ -olefin homopolymers or interpolymers, thermoplastic polyolefms (TPOs), engineering thermoplastics, styrenic block copolymers, elastomers, and the vinyl or vinylidene halide homopolymers and copolymers.
  • TPOs thermoplastic polyolefms
  • engineering thermoplastics styrenic block copolymers
  • elastomers elastomers
  • vinyl or vinylidene halide homopolymers and copolymers ethylene and/or ⁇ -olefin homopolymers or interpolymers.
  • TPOs thermoplastic polyolefms
  • styrenic block copolymers elastomers
  • the coatings of the present invention can optionally further comprise (C) a solvent system and (D) one or more other additives including, but not limited to, binders, thinners, adhesion promoters, fillers, tackifiers and processing aids, surfactants, hardening resins and other surface modifying additives.
  • the substantially random interpolymers used to prepare the coating compositions of the present invention include interpolymers prepared by polymerizing ethylene and/or one or more ⁇ -olefins with one or more vinyl or vinylidene aromatic monomers and/or one or more sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, and optionally other polymerizable monomers.
  • Suitable ⁇ -olefins includes for example, ⁇ -olefins containing from 3 to about 20, preferably from 3 to 12, more preferably from 3 to 8 carbon atoms. Particularly suitable are propylene, butene-1, 4-methyl-l-pentene, heptene-1, hexene-1 or octene- 1. Also suitable is ethylene in combination with one or more ⁇ -olefins containing from 3 to 20 carbon atoms, and particularly ethylene in combination with one or more selected from propylene. butene-1, pentene-1, 4-methyl-l-pentene, hexene-1, heptene- 1 or octene-1. These ⁇ -olefins do not contain an aromatic moiety.
  • strained ring olefins such as norbornene and C,. I0 alkyl or C 6 . 10 aryl substituted norbornenes, with an exemplary interpolymer being ethylene/styrene/norbornene.
  • Suitable vinyl or vinylidene aromatic monomers include, for example, those represented by the following formula:
  • R l — C C(R 2 ) 2
  • R' is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C -alkyl, and C -haloalkyl
  • n has a value from zero to 4, preferably from zero to 2, most preferably zero.
  • Exemplary vinyl aromatic monomers include styrene, vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene. including all isomers of these compounds,. Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof. Preferred monomers include styrene, ⁇ -methyl styrene, the lower alkyl- (C, - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-. meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof,. A more preferred aromatic vinyl monomer is styrene.
  • R l _ C C(R 2 ) 2
  • a 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R 1 and A' together form a ring system.
  • Preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted.
  • substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, tert-butyl, norbornyl,.
  • Most preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene. Especially suitable are 1-, 3-, and 4-vinylcyclohexene. ⁇ -Olefin monomers containing from 3 to 20 carbon atoms and having a linear aliphatic structure such as propylene, butene-1, hexene-1 and octene-1 are not considered as hindered aliphatic monomers.
  • the substantially random interpolymers may be modified by typical grafting, hydrogenation, functionalizing, or other reactions well known to those skilled in the art. This includes maleic anhydride- HDPE-,and polypropylene-grafted substantially random interpolymers.
  • the substantially random interpolymers may also be readily sulfonated or chlorinated to provide functionalized derivatives according to established techniques.
  • One method of preparation of the substantially random interpolymers includes polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts.
  • the substantially random interpolymers include the pseudo random interpolymers prepared and described in EP-A-0,416,815 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J. Timmers.
  • Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from -50°C to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization.
  • substantially random ⁇ -olefin/vinyl aromatic interpolymers can also be prepared by the methods described in JP 07/278230 employing compounds shown by the general formula
  • Cp 1 and Cp 2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents of these, independently of each other;
  • R 1 and R 2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1-12, alkoxyl groups, or aryloxyl groups, independently of each other;
  • M is a group IV metal, preferably Zr or Hf. most preferably Zr; and R 3 is an alkylene group or silanediyl group used to crosslink Cp' and Cp 2 ).
  • the substantially random ⁇ -olefin/vinyl aromatic interpolymers can also be prepared by the methods described by John G. Bradfute et al. (W. R. Grace & Co.) in WO 95/32095; by R. B. Pannell (Exxon Chemical Patents, Inc.) in WO 94/00500; and in Plastics Technology, p. 25 (September 1992).
  • substantially random interpolymers which comprise at least one ⁇ -olefin/vinyl aromatic/vinyl aromatic/ ⁇ -olefin tetrad disclosed in U. S. Application No. 08/708.809 filed September 4. 1996 by Francis J. Timmers et al.
  • These interpolymers contain additional signals in their carbon- 13 NMR spectra with intensities greater than three times the peak to peak noise. These signals appear in the chemical shift range 43.70 - 44.25 ppm and 38.0 - 38.5 ppm. Specifically, major peaks are observed at 44.1, 43.9. and 38.2 ppm.
  • a proton test NMR experiment indicates that the signals in the chemical shift region 43.70 - 44.25 ppm are methine carbons and the signals in the region 38.0 - 38.5 ppm are methylene carbons.
  • these new signals are due to sequences involving two head- to-tail vinyl aromatic monomer insertions preceded and followed by at least one ⁇ - olefin insertion, for example an ethylene/styrene/styrene/ethylene tetrad wherein the styrene monomer insertions of said tetrads occur exclusively in a 1 ,2 (head to tail) manner.
  • interpolymers can be prepared by conducting the polymerization at temperatures of from -30°C to 250°C in the presence of such catalysts as those represented by the formula
  • suitable substituted cyclopentadien is
  • each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group.
  • R independently each occurrence is (including where appropriate all isomers) hydrogen, methyl, ethyl, propyl.
  • catalysts include, for example, racemic- (dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)zirconium dichloride. racemic- (dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)zirconium 1 ,4-diphenyl- 1 ,3- butadiene, racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)zirconium di- Cl-4 alkyl, racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl) zirconium di-Cl-4 alkoxide. or any combination thereof.
  • titanium-based constrained geometry catalysts [N-(l.l-dimethylethyl)-l,l-dimethyl-l-[(l,2,3,4,5- ⁇ )-l,5,6,7-tetrahydro-s- indacen-l-yl]silanaminato(2-)-N]titanium dimethyl; (l-indenyl)(tert-butylamido) dimethyl- silane titanium dimethyl; ((3-tert-butyl)(l,2,3,4,5- ⁇ )-l-indenyl)(tert- butylamido) dimethylsilane titanium dimethyl; and ((3-iso-propyl)(l,2,3.4,5- ⁇ )-l- indenyl)(tert-butyl amido)dimethylsilane titanium dimethyl, or any combination thereof.
  • ⁇ -olefin/vinyl aromatic monomer inte ⁇ olymers such as propylene/styrene and butene/styrene are described in United States patent number 5,244,996, issued to Mitsui Petrochemical Industries Ltd or United States patent number 5,652,315 also issued to Mitsui Petrochemical Industries Ltd or as disclosed in DE 197 11 339 A 1 to Denki Kagaku Kogyo KK.
  • the random copolymers of ethylene and styrene as disclosed in Polymer Preprints Vol 39, No. 1, March 1998 by Toru Aria et al. can also be employed as blend components of the present invention.
  • the products of hydrogenation of random polymers of vinyl or vinylidene aromatic and diene monomers including but not limited to random styrene butadiene or styrene/isoprene copolymers.
  • the coatings of the present invention can further comprise one or more additional resin components (Component B) selected from the group consisting of styrenic homopolymers or copolymers, ethylene and/or ⁇ -olefin homopolymers or inte ⁇ olymers, thermoplastic polyolefms (TPOs), engineering thermoplastics, styrenic block copolymers, elastomers, and the vinyl or vinylidene halide homopolymers and copolymers.
  • Component B selected from the group consisting of styrenic homopolymers or copolymers, ethylene and/or ⁇ -olefin homopolymers or inte ⁇ olymers, thermoplastic polyolefms (TPOs), engineering thermoplastics, styrenic block copolymers, elastomers, and the vinyl or vinylidene halide homopolymers and copolymers.
  • the styrenic homopolymers or copolymers employed as component (B) of the coating compositions of the present invention are polymers of vinyl or vinylidene aromatic monomers and include homopolymers or copolymers of one or more vinyl or vinylidene aromatic monomers, or an copolymer of one or more vinyl or vinylidene aromatic monomers and one or more monomers copolymerizable therewith other than an aliphatic ⁇ -olefin.
  • Suitable vinyl or vinylidene aromatic monomers are represented by the following formula:
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing three carbons or less
  • Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C - alkyl, and C M -haloalkyl.
  • Exemplary vinyl or vinylidene aromatic monomers include styrene, para-vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, etc.
  • Styrene is a particularly desirable vinyl aromatic monomer for the vinyl aromatic polymers used in the practice of the present invention.
  • a preferred polymer is atactic polystyrene. While preparing the substantially random inte ⁇ olymer component (A) of the present invention, atactic vinyl aromatic homopolymer may be formed due to homopolymerization of the vinyl aromatic monomer at elevated temperatures. For the pu ⁇ ose of the present invention, the atactic vinyl aromatic homopolymer, typically atactic polystyrene, constitutes at least part of the immiscible blend component (B).
  • Suitable copolymerizable comonomers in Component (B), other than a vinyl or vinylidene aromatic monomer include, for example, C 4 -C 6 conjugated dienes, especially butadiene or isoprene, n-phenyl maleimide, acrylamide.
  • ethylenically- unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, ethylenically- unsaturated mono- and difunctional carboxylic acids and derivatives thereof such as esters and, in the case of difunctional acids, anhydrides, such as acrylic acid, C,_,- alkylacrylates or methacrylates.
  • the polymers of vinyl or vinylidene aromatic monomers with other copolymerizable comonomers preferably contain, polymerized therein, at least 50 percent by weight and, preferably, at least 65 percent by weight of one or more vinyl or vinylidene aromatic monomers.
  • styrenic copolymers are styrene/acrylonitrile (SAN) copolymers, styrene/maleic anhydride copolymers (SMA), styrene/methyl methacrylate copolymers (S-MMA) and the rubber modified copolymers such as acrylonitrile/butadiene/styrene copolymer (ABS).
  • the number average molecular weight M n of the styrenic homopolymers and copolymers used as blend components of the present invention is from 1000 to 1,000,000, preferably from 5,000 to 500.000, even more preferably from 10,000 to 350,000, and the molecular weight distribution M Mn is from 1.005 to 20.000.
  • Rubber modified vinyl aromatic polymers can be prepared by polymerizing the vinyl aromatic monomer in the presence of a predissolved rubber to prepare impact modified, or grafted rubber containing products, examples of which are described in US patents 3,123,655, 3,346,520, 3,639,522, and 4,409,369.
  • the rubber is typically a butadiene or isoprene rubber, preferably polybutadiene.
  • the rubber modified vinyl aromatic polymer is high impact polystyrene (HIPS).
  • Component (B) may also be a flame resistant rubber modified styrenic blend composition.
  • the flame resistant compositions are typically produced by adding flame retardants to a high impact polystyrene (HIPS) resin.
  • IRPS ignition resistant polystyrene
  • Suitable polymers to be employed as component (B) also include vinyl or vinylidene aromatic polymers having a high degree of isotactic or syndiotactic configuration.
  • a high degree of syndiotactic configuration is meant that the stereochemical structure is mainly of syndiotactic configuration, the stereostructure in which phenyl groups or substituted phenyl group as side chains are located alternately at opposite directions relative to the main chain consisting of carbon-carbon bonds. Tacticity is quantitatively determined by the 13C-nuclear magnetic resonance method, as is well known in the art.
  • the degree of syndiotacticity as measured by 13C NMR spectroscopy is greater than 75 percent r diad, more preferably greater than 90 percent r diad.
  • Suitable examples of syndiotactic polymers include polystyrene, poly(alkylstyrene), poly(halogenated styrene), poly(alkoxystyrene), poly(vinylbenzoate), the mixtures thereof, and copolymers containing the above polymers as main components.
  • Poly(alkylstyrene) includes poly(methylstyrene), poly(ethylstyrene) poly(isopropylstyrene), poly(tert-butylstyrene), etc.
  • Poly(halogenated styrene) includes, poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene), etc.
  • Poly(alkoxystyrene) includes, poly(methoxystyrene), poly(ethoxystyrene), etc.
  • Preferred styrenic copolymers having tacticity and employed as component (B) are syndiotactic polystyrene (SPS) which usually has a weight-average molecular weight of 10,000 to 10,000,000, preferably 100,000 to 5,500,000 with a number-average molecular weight of 5,000 to 5,500,000, preferably 50,000 to 2,500,000.
  • SPS syndiotactic polystyrene
  • the syndiotactic polymer has a melting point of 160 to 310°C.
  • the ethylene and/or ⁇ -olefin homopolymers or inte ⁇ olymers can also be employed as component (B) of the coating compositions of the present invention. These are inte ⁇ olymers comprising ethylene and or C 3 -C 20 ⁇ - olefins.
  • the ⁇ -olefin homopolymers and inte ⁇ olymers include polypropylene, propylene/C 4 -C 20 ⁇ - olefin copolymers, polyethylene, and ethylene/C 3 -C 20 ⁇ - olefin copolymers.
  • the inte ⁇ olymers can be either heterogeneous ethylene/ ⁇ -olefin inte ⁇ olymers or homogeneous ethylene/ ⁇ -olefin inte ⁇ olymers. including the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers.
  • Suitable aliphatic ⁇ -olefin monomers which introduce polar groups into the polymer include, for example, ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile.
  • ethylenically unsaturated anhydrides such as maleic anhydride
  • ethylenically unsaturated amides such as acrylamide, methacrylamide etc.
  • ethylenically unsaturated carboxylic acids both mono- and difunctional
  • esters especially lower, for example C,-C 6 , alkyl esters
  • ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethyl acrylate, hydroxyethylacrylate, n-butyl acrylate or methacrylate, 2-ethyl- hexylacrylate etc.
  • ethylenically unsaturated dicarboxylic acid imides such as N- alkyl or N-aryl maleimides such as N-phenyl maleimide, etc.
  • Such monomers containing polar groups are acrylic acid, vinyl acetate, maleic anhydride and acrylonitrile.
  • exemplary polymer are ethylene vinyl acetate (EVA) and ethylene vinyl alcohol (EVOH).
  • Halogen groups which can be included in the polymers from aliphatic ⁇ -olefin monomers include fluorine, chlorine and bromine; preferably such polymers are chlorinated polyethylenes (CPEs).
  • Heterogeneous inte ⁇ olymers are differentiated from the homogeneous inte ⁇ olymers in that in the latter, substantially all of the inte ⁇ olymer molecules have the same ethylene/comonomer ratio within that inte ⁇ olymer, whereas heterogeneous inte ⁇ olymers are those in which the inte ⁇ olymer molecules do not have the same ethylene/comonomer ratio.
  • heterogeneous inte ⁇ olymers The term “broad composition distribution” used herein describes the comonomer distribution for heterogeneous inte ⁇ olymers and means that the heterogeneous inte ⁇ olymers have a "linear" fraction, multiple melting peaks (that is, exhibit at least two distinct melting peaks) by DSC and have a degree of branching less than or equal to 2 methyls/ 1000 carbons in 10 percent (by weight) or more, preferably more than 15 percent (by weight), and especially more than 20 percent (by weight of the polymer).
  • the heterogeneous inte ⁇ olymers also have a degree of branching equal to or greater than 25 methyls/ 1000 carbons in 25 percent or less (by weight of the polymer), preferably less than 15 percent (by weight), and especially less than 10 percent (by weight of the polymer).
  • the Ziegler catalysts suitable for the preparation of the heterogeneous component of the current invention are typical supported, Ziegler-type catalysts which are particularly useful at the high polymerization temperatures of the solution process.
  • Examples of such compositions are those derived from organomagnesium compounds, alkyl halides or aluminum halides or hydrogen chloride, and a transition metal compound. Examples of such catalysts are described in U.S. Pat Nos. 4,314,912 (Lowery, Jr. et al.), 4,547,475 (Glass et al.), and 4,612,300 (Coleman, III.
  • Suitable catalyst materials may also be derived from a inert oxide supports and transition metal compounds. Examples of such compositions suitable for use in the solution polymerization process are described in U.S. Pat No. 5,420,090 (Spencer, et al).
  • the heterogeneous polymer component can be an ethylene and/or ⁇ -olefin homopolymer preferably polyethylene or polypropylene, or, preferably, an inte ⁇ olymer of ethylene with at least one C3-C20 oc-olefin and/or C4- 8 diolefins.
  • Heterogeneous copolymers of ethylene and 1-butene, ethylene and 1-pentene, ethylene and 1-hexene and ethylene and 1-octene are especially preferred.
  • ethylene inte ⁇ olymers Such polymers are known as homogeneous inte ⁇ olymers and are characterized by their narrower molecular weight and composition distributions relative to, for example, traditional Ziegler catalyzed heterogeneous polyolefin polymers.
  • Substantially linear ethylene/ ⁇ -olefin polymers and inte ⁇ olymers which can be employed as component (B) of the present invention are herein defined as in U.S. Patent No. 5,272,236 (Lai et al.), and in U.S. Patent No. 5,278,272.
  • the homogeneous polymer component can be an ethylene and/or ⁇ -olefin homopolymer preferably polyethylene or polypropylene, or, preferably, an inte ⁇ olymer of ethylene with at least one C3-C20 ⁇ -olefin and/or C4-C18 diolefins. Homogeneous copolymers of ethylene and one or more C3-C8 ⁇ -olefins are especially preferred.
  • ultralow density polyethylene ULDPE
  • low density polyethylene LDPE
  • linear low density polyethylene LLDPE
  • medium density polyethylene MDPE
  • high density polyethylene HDPE
  • polyolefin plastomers such as those marketed by The Dow Chemical Company under the AFFINITYTM tradename and polyethylene elastomers, such as those marketed under the ENGAGETM tradename by Du Pont Dow Elastomers PLC.
  • the molecular weight of the ethylene homopolymers and inte ⁇ olymers for use in the present invention is conveniently indicated using a melt flow measurement according to ASTM D-1238, Condition 190°C/2.16 kg (formerly known as "Condition (E)" and also known as I 2 ).
  • melt flow rate is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt flow rate, although the relationship is not linear.
  • the melt flow rate (12, ASTM D-1238, Condition 190°C/2.16 kg) for the ethylene homopolymers and inte ⁇ olymers useful herein is generally from 0.1 grams/ 10 minutes (g/10 min) to 1000 g/10 min, preferably from 0.5 g/10 min to 200 g/10 min, and especially from 1 g/10 min to 100 g/10 min.
  • the C3 ⁇ -olefin homopolymers or copolymers employed as component (B) of the coating compositions of the present invention are polypropylenes.
  • the polypropylene is generally in the isotactic form of homopolymer polypropylene, although other forms of polypropylene can also be used (for example, syndiotactic or atactic).
  • Polypropylene impact copolymers for example, those wherein a secondary in-reactor copolymerization step reacting ethylene with the propylene is employed
  • random copolymers also reactor modified and usually containing 1.5-20 percent of ethylene or C4-C8 ⁇ -olefin copolymerized with the propylene
  • a complete discussion of various polypropylene polymers is contained in
  • the melt flow rate for the polypropylene useful herein is generally from 0.5 grams/ 10 minutes (g/10 min) to 200 g/10 min, preferably from 1.0 g/10 min to 100 g/10 min, and especially from 2 g/10 min to 50 g/10 min.
  • the thermoplastic polyolefms (TPOs) employed as component (B) of the coating compositions of the present invention are generally produced from propylene homo- or copolymers as described above, or blends of an elastomeric material such as ethylene/propylene rubber (EPM) or ethylene/propylene diene monomer te ⁇ olymer (EPDM) and a more rigid material such as isotactic polypropylene. Other materials or components can be added into the formulation depending upon the application, including oil, fillers, and cross-linking agents. In-reactor TPO's can also be used as blend components of the present invention.
  • thermoplastics can also be employed as Component (B) of the coating compositions of the present invention.
  • Component (B) of the coating compositions of the present invention.
  • Engineering thermoplastics which can be employed as blend component (B) include polyoxymethylene-based resins such as acetal; acrylic resins (for example poly(methylmethacrylate, PMMA)); polyamides (for example nylon-4,6, nylon-6, nylon 6,6, and higher nylons), polyimides, polyetherimides, cellulosics, polyesters, poly(arylate); aromatic polyesters (for example polybutylene terephthalate and polyethylene terephthalate, and polycarbonate); liquid crystal polymers; blends, or alloys of the foregoing resins; and other resin types including for example rigid thermoplastic polyurethanes; high temperature polyolefms such as ethylene/norbornene copolymers, polycyclopentanes, its copolymers, and polymethylpentane and its copolymers.
  • polyoxymethylene-based resins such as acetal; acrylic resins (for example poly(methylmethacrylate, PMMA)); polyamides (for example nylon-4,6, nylon-6, nylon
  • aromatic polyethers including, for example, the poly(phenylene ether) (PPE) thermoplastic engineering resins which are well known, commercially available materials produced by the oxidative coupling polymerization of alkyl substituted phenols. They are generally linear, amo ⁇ hous polymers having a glass transition temperature in the range of 190°C to 235°C.
  • PPE materials include those represented by the formula:
  • Q is the same or different alkyl group having from 1 to 4 carbon atoms and n is a whole integer of at least 100, preferably from 150 to 1200.
  • preferred polymers are poly(2,6-dialkyl-l,4-phenylene ether) such as poly(2,6-dimethyl-l,4- phenylene ether), poly(2-methyl-6-ethyl-l ,4-phenylene ether), poly(2-methyl-6- propyl-l,4-phenylene ether), poly-(2,6-dipropyl-l,4-phenylene ether) and poly (2- ethyl-6-propyl-l ,4-phenylene ether).
  • a more preferred polymer is poly(2,6-dimethyl- 1 ,4-phenylene ether). These polymers are often sold as blends with polystyrene and high impact polystyrene, and other formulation components.
  • Especially preferred engineering thermoplastics are acetal, polymethylmethacrylate,. poly(phenylene oxide), nylon-6, nylon 6,6, bisphenol A- poly(carbonate), poly(2,6-dimethyl-l,4-phenylene ether), and polybutylene terephthalate and polyethylene terephthalate,
  • Styrenic block copolymers which can be employed as component (B) of the coating compositions of the present invention are those having unsaturated rubber monomer units including, but not limited to, styrene-butadiene (SB), styrene- isoprene(SI), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), ⁇ - methylstyrene-butadiene- ⁇ -methylstyrene and ⁇ -methylstyrene-isoprene- ⁇ - methylstyrene.
  • SB styrene-butadiene
  • SI styrene-isoprene
  • SI styrene-butadiene
  • SIS styrene-isoprene-styrene
  • the styrenic portion of the block copolymer is preferably a polymer or copolymer of styrene and its analogs and homologs including ⁇ -methylstyrene and ring-substituted styrenes, particularly ring-methylated styrenes.
  • the preferred styrenics are styrene and ⁇ -methylstyrene, and styrene is particularly preferred.
  • Block copolymers with unsaturated rubber monomer units may comprise homopolymers of butadiene or isoprene or they may comprise copolymers of one or both of these two dienes with a minor amount of styrenic monomer.
  • Preferred styrenic block copolymers which can be employed as Component (B) include at least one segment of a styrenic unit and at least one segment of an ethylene-butene or ethylene-propylene copolymer.
  • block copolymers with saturated rubber monomer units examples include styrene/ethylene-butene copolymers, styrene/ethylene-propylene copolymers, styrene/ethylene-butene/styrene (SEBS) copolymers, styrene/ethylene-propylene/styrene (SEPS) copolymers.
  • SEBS styrene/ethylene-butene copolymers
  • SEBS styrene/ethylene-propylene copolymers
  • SEPS styrene/ethylene-propylene/styrene
  • the elastomers which can be employed as component (B) of the coating compositions of the present invention include, but are not limited to, rubbers such as polyisoprene, polybutadiene, natural rubbers, ethylene/propylene rubbers, ethylene/propylene diene (EPDM) rubbers, silicone rubbers, styrene/butadiene rubbers and thermoplastic polyurethanes.
  • rubbers such as polyisoprene, polybutadiene, natural rubbers, ethylene/propylene rubbers, ethylene/propylene diene (EPDM) rubbers, silicone rubbers, styrene/butadiene rubbers and thermoplastic polyurethanes.
  • the vinyl or vinylidene halide polymer component of the blends of the present invention include but are not limited to homopolymers and copolymers of vinyl or vinylidene halides with copolymerizable monomers such as ethylene and/or ⁇ -olefins including but not limited to ethylene, propylene, vinyl esters of organic acids containing 1 to 18 carbon atoms, for example vinyl acetate, vinyl stearate and so forth; vinyl chloride, vinylidene chloride, symmetrical dichloroethylene; acrylonitrile, methacrylonitrile; alkyl acrylate esters in which the alkyl group contains 1 to 8 carbon atoms, for example methyl acrylate and butyl acrylate; the corresponding alkyl methacrylate esters; dialkyl esters of dibasic organic acids in which the alkyl groups contain 1 - 8 carbon atoms, for example dibutyl fumarate. diethyl maleate, and so forth.
  • the vinyl or vinylidene halide polymers are homopolymers or copolymers of vinyl chloride or vinylidene chloride.
  • Poly (vinyl chloride) polymers PVC
  • PVC poly (vinyl chloride) polymers
  • Flexible PVC is distinguished from rigid PVC primarily by the presence of and amount of plasticizers in the resin. Flexible PVC typically has improved processability, lower tensile strength and higher elongation than rigid PVC.
  • PVDC vinylidene chloride homopolymers and copolymers
  • typically the copolymers with vinyl chloride, acrylates or nitriles are used commercially and are most preferred.
  • the choice of the comonomer significantly affects the properties of the resulting polymer. Perhaps the most notable properties of the various PVDC's are their low permeability to gases and liquids, barrier properties; and chemical resistance.
  • CPVC chlorinated PVC
  • CPVC chlorinated PVC
  • Optimal adhesion occurs when the solvent system a good solvent for both the coating polymer and the substrate, the more critical being the extent of substrate solvency.
  • the coating formulation's percent solids, hiding, coating thickness is affected by viscosity and thus coating polymer solubility. Solvent selections for both coating polymer and substrate polymer should thus be made after determining percent solids and/or minimum viscosity trends for each pure material or material blend. Optimized solubility of both the coating polymer and substrate polymer corresponds with the most durable, measured adhesion.
  • Solvents in the formulation should include a high boiling aromatic solvent for ethylene-styrene substrates.
  • a solvent which softens/swells the interface of the plastic substrate is also preferred.
  • optimal adhesion occurs when the solvent system is a good solvent for both the coating polymer (binder component) and the substrate, the more critical being the extent of substrate solubility.
  • the coating formulation's percent solids, hiding ability, coating thickness is affected by viscosity, and thus coating polymer solubility, and thus the coating adhesion does not only correlate with the solubility parameter.
  • solvents such as toluene generally give the lowest viscosity coating formulations and thus have potential for higher percent solids, better surface coverage, substrate hiding, and gloss. Better surface coverage and substrate hiding typically result from coating formulations of higher percent solids.
  • the preferred high boiling solvents include toluene, and aromatic petroleum fractions boiling between 30 and 200°C, preferably propylbenzene and its isomers and isomers of butylbenzene.
  • aqueous-based systems comprising water as the solvent may also be used.
  • Such systems may also comprise a surfactant system to facilitate wetting of the substrate and wetting and dispersion of the binder.
  • Such systems may also include the additional additives used to enhance the properties of coatings as described herein.
  • Processing aids which are also referred to herein as plasticizers, employed as Component D of the coating compositions of the present invention, include the phthalates, such as dioctyl phthalate and diisobutyl phthalate.
  • natural oils such as lanolin, and paraffin, naphthenic and aromatic oils obtained from petroleum refining, and liquid resins from rosin or petroleum feedstocks.
  • Exemplary classes of oils useful as processing aids include white mineral oil (such as KaydolTM oil (available from and a registered trademark of Witco), and ShellflexTM 371 naphthenic oil (available from and a registered trademark of Shell Oil Company).
  • Another suitable oil is TufloTM oil (available from and a registered trademark of Lyondell).
  • Hydrocarbon resins most typically used as tackifiers in rubber compounding, can be added into the ESI and/or Kraton coatings which increase coating hardness, as measured by scratch resistance, without sacrificing flexibility and with improved adhesion to ESI substrates. Scratch resistance and compatibility were less in Kraton styrene block copolymers.
  • the hydrocarbon resins are more advantageous to use, therefore, in ESI based coatings.
  • the additives include, for example, coumarone- indene resins of glass transition temperatures greater than polystyrene, or other high glass transition temperature resins that associate with polystyrene endblocks.
  • the tackifying resins should be completely compatible with coating solvents, dispersant(s), and other additives for optimal gloss, surface hardness, and adhesion.
  • the preferred glass transition temperatures (T g ) of the tackifying resins are between 120 and 172°C. Lower T g resins do not appreciably harden the surface but still improve adhesion. Specifically higher T g resins (above 160°C) tend to be less compatible with Kraton, or styrene block copolymers. Compatibility, indicated by a clear solution of the tackifying resin with coating polymer, was necessary for improved surface hardness. Surface hardness was measured by a gloss change after abrasion.
  • a suitable tackifier may be selected on the basis of the criteria outlined by Hercules in J. Simons, Adhesives Age, "The HMDA Concept: A New Method for Selection of Resins", November 1996. This reference discusses the importance of the polarity and molecular weight of the resin in determining compatibility with the polymer.
  • preferred-tackifiers will have some degree of aromatic character to promote compatibility, particularly in the case of substantially random inte ⁇ olymers having a high content of the vinyl aromatic monomer.
  • Tackifying resins can be obtained by the polymerization of petroleum and te ⁇ ene feedstreams and from the derivatization of wood, gum, and tall oil rosin.
  • tackifiers include wood rosin, tall oil and tall oil derivatives, and cyclopentadiene derivatives, such as are described in United Kingdom patent application GB 2,032,439A.
  • Other classes of tackifiers include aliphatic C5 resins, polyte ⁇ ene resins, hydrogenated resins, mixed aliphatic-aromatic resins, rosin esters, natural and synthetic te ⁇ enes, te ⁇ ene- phenolics, and hydrogenated rosin esters.
  • Component D of the coating compositions of the present invention are the various organic and inorganic fillers, the identity of which depends upon the type of application for which the elastic film is to be utilized.
  • the fillers can also be included in either blend Component A and/or blend Component B or the overall blend compositions employed to prepare the fabricated articles of the present invention.
  • fillers include organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers), talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate, glass fibers, marble dust, cement dust, clay, feldspar, silica or glass, fumed silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, aluminum nitride, B 2 O 3 , nickel powder or chalk.
  • organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers), talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate, glass fibers, marble dust, cement dust, clay, feldspar, silica or glass, fumed silic
  • organic or inorganic, fiber or mineral, fillers include carbonates such as barium, calcium or magnesium carbonate; fluorides such as calcium or sodium aluminum fluoride; hydroxides such as aluminum hydroxide; metals such as aluminum, bronze, lead or zinc; oxides such as aluminum, antimony, magnesium or zinc oxide, or silicon or titanium dioxide; silicates such as asbestos, mica, clay (kaolin or calcined kaolin), calcium silicate, feldspar, glass (ground or flaked glass or hollow glass spheres or microspheres or beads, whiskers or filaments). nepheline, perlite.
  • nanofillers include, but are not limited to, talc, clays such as montmorillonite and other aluminosilicates. mixed - metal and/or double layered hydroxides, mica, and organically treated analogs of said nanofillers.
  • Component D of the coating compositions of the present invention are hardening resins that associate with the styrene units in the polymer components and like the nanofillers, may be added to improve gloss and scratch resistance, for example, coumarone-indene, polystyrene, or polymethylstyrene resins.
  • Component D of the coating compositions of the present invention are the traditional coating binders which include, but are not limited to, styrne block copolymers, styrene acrylic copolymers, epoxies and epoxy hybrids, polyurethanes and polyurethane hybrids, polyesters, and acrylics.
  • compositions of the present invention include colorants, organic and/or inorganic pigments, dispersing agents and/or resins, and surface control additives commonly used in coatings.
  • surface control additives include anti-foam, surface leveling, and mar-slip additives.
  • antioxidants for example, hindered phenols such as, for example, Irganox® 1010 a registered trademark of Ciba Geigy
  • phosphites for example, Irgafos® 168 a registered trademark of Ciba Geigy
  • UN. stabilizers antistatic agents (for example the quaternary ammonium salts), cling additives (for example, polyisobutylene), slip agents (such as erucamide and/or stearamide), antiblock additives
  • additives are employed in functionally equivalent amounts known to those skilled in the art.
  • the amount of antioxidant employed is that amount which prevents the polymer or polymer blend from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers.
  • Such amount of antioxidants is usually in the range of from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percent by weight based upon the weight of the polymer or polymer blend.
  • the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer or polymer blend antiblocking, to produce the desired result, to provide the desired color from the colorant or pigment.
  • Such additives can suitably be employed in the range of from 0.05 to 50, preferably from 0.1 to 35, more preferably from 0.2 to 20 percent by weight based upon the weight of the polymer or polymer blend.
  • the substrates to be covered by the coatings of the present invention include the normal materials of fabrication for articles to be painted, including metals, wood paper, glass, cement and masonry.
  • the substrates can also be the various plastics and can include, but are not limited to, substantially random ethylene/styrene inte ⁇ olymers, one or more styrenic homopolymers or copolymers, ethylene and/or ⁇ - olefin homopolymers or copolymers, thermoplastic polyolefms, engineering thermoplastics, styrenic block copolymers, elastomers, or vinyl halide polymers, and blend combinations thereof.
  • Such paint formulations are typically prepared in a two-step operation involving separate preparation of a "millbase” and a “ letdown” .
  • a typical millbase formulation is shown in Table 1. Table 1 Plastics Coating; Formulation Millbase
  • the ingredients are typically mixed in the following order; solvents, polymer and dispersants first, then pigment.
  • the millbase is ground using a ball mill or similar pigment grinding apparatus to produce a fine dispersion of pigment, approximate particle size less than 37.5 ⁇ m as measured by a Hegman blade gauge. Millbase is used to disperse pigments for adding color or matting effects into the coating formulation.
  • Typical wetting agents include maleic anhydride, trimellitic anhydride, or a naphthalenesulfonate.
  • Dispersing resins as commonly used for styrene-acrylic coatings are ideal and produce high gloss, especially when the dispersant polarity was properly matched with the coating polymer (ESI or Kraton).
  • some coating polymer (ESI or Kraton) or hardening additive in addition to the dispersing resins are typically added into the millbase to improve the millbase viscosity.
  • the resins also contribute additional dispersion stability in a steric fashion, preventing pigment particle re- flocculation during the grinding process, thus accelerating the grinding process.
  • letdown is produced separately and then blended with the millbase. Alternatively, the letdown may be applied alone as a clear coating. Overall percent solids of the coating formulation is 15 to 25 percent by weight. Lower percent solids are more conducive for spray application. Sufficient solvent must be used in the letdown to produce a clear, non-hazy solution of polymer or gloss will be affected. Pigment volume concentration (PVC) should be less than 15 percent of the coating solids to produce gloss (60°) values of 60 and less than 25 percent coating solids to produce gloss (60°) values of 20. Larger pigment volumes produce flatted films (60° gloss values near 0).
  • Relative weight ratios can be changed depending on the coating processing and desired viscosity and percent solids. For example, less polymer (resin) may be added to the grind stage by instead adding during the letdown (pigmented coatings), or more pigment can be used to make a less glossy coating but which then requires more dispersant. or less polymer may be used in the letdown to reduce viscosity.
  • a typical letdown formulation is shown in Table 2.
  • Dispersing resins as commonly used for styrene-acrylic coatings tend to be ideal, producing optimum gloss.
  • Millbase ingredients are mixed, solvents, polymer and dispersants first, then pigment.
  • the millbase is ground using a ball mill or similar pigment grinding apparatus to produce a fine dispersion of pigment, approximate particle size less than 37 ⁇ m ( ⁇ 1.5 mil) as measured by a Hegman blade gauge.
  • Millbase is used to disperse pigments for adding color or matting effects into the coating formulation.
  • Wetting agents typically comprise maleic anhydride, trimellitic anhydride, or a naphthalenesulfonate .
  • substantially random inte ⁇ olymers give the lowest formulation viscosity and therefore can be formulated to higher percent solids than inte ⁇ olymers of lower melt index. Increasing the vinyl aromatic concentration in the substantially random inte ⁇ olymers lowers formulation viscosity by improving polymer solubility, allowing coating formulations of higher percent solids.
  • the substantially random inte ⁇ olymer can be the major resin component of the formulation or can be present as a minor resin component for example when being used as an adhesion promoter especially when the substrates to be painted are themselves comprised of substantially random inte ⁇ olymers.
  • the substantially random inte ⁇ olymer is present in the wet aqueous or solvent-based coating formulation from 0.1 to 100 wt percent (in the case of a dry that is solvent free formulation) preferably from 0.1 to 50, preferably from 1 to 30, most preferably from 1 to 20 wt percent based on the total weight of the formulation.
  • the preferred substantially random inte ⁇ olymers contain from 0.5 mol percent to 65 mol percent (80 wt percent), preferably from 5 to 65 more preferably from 15 to 65 mole percent of at least one vinyl or vinylidene aromatic monomer and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer and from 35 to 99.5, preferably from 35 to 95, more preferably from 35 to 85 mole percent of ethylene and/or at least one aliphatic ⁇ -olefin having from 3 to 20 carbon atoms.
  • the melt index (12) of the substantially random inte ⁇ olymer used in the paint formulations of the present invention is from 0.1 to 1000, preferably of from 1 to 500 more preferably of from 5 to 200 g/10 min.
  • the molecular weight distribution (M M of the substantially random inte ⁇ olymer used to prepare the elastic films of the present invention is from 1.5 to 20, preferably of from 1.8 to 10, more preferably of from 2 to 5.
  • coatings of the present invention can further comprise an additional resin selected from the group consisting of styrenic block copolymers, polyurethanes, acrylics pigment(s), tackifiers and surface modifying additives.
  • the preferred solvents include water, toluene and high boiling aromatic petroleum fractions preferably boiling between 30 and 200°C, and more preferably propylbenzene and its isomers and isomers of butylbenzene.
  • the water or solvent component is present in the wet aqueous or solvent-based coating formulation from 50 to 99.9, preferably from 70 to 99, most preferably from 80 to 99 wt percent based on the total weight of wet formulation.
  • the substantially random inte ⁇ olymers can be used as an additive in existing solvent borne coating formulations, functioning as an adhesion promoter to low surface energy plastic substrates, such as ethylene-styrene copolymers or polyethylene, polystyrene, polypropylene, ABS, and other olefinic and styrenic substrates.
  • the preferred ethylene-styrene inte ⁇ olymers include, but are not limited to, compositions of 20 to 80 percent styrene by weight of total monomer with a melt index (12) of between 0.1 and 200.
  • Higher melt index polymers give the lowest formulation viscosity and therefore can be formulated to higher percent solids than polymers of lower melt index.
  • Increasing the styrene concentration in the polymer improves polymer solubility, also allowing coating formulations of higher percent solids.
  • Styrene content also improves gloss and pigment dispersion stability.
  • Glass transition temperature of the coating polymer has little affect on adhesion to the ethylene-styrene copolymer substrate, but does affect coating scratch resistance and flexibility.
  • higher glass transition temperature polymers ⁇ 20°C
  • Rubbing with white paper does not affect gloss and, for pigmented systems, can instead improve gloss due to a burnishing effect. Practical coating flexibility at temperatures lower than the glass transition temperature is marginal.
  • coatings for ethylene-styrene inte ⁇ olymer substrates with enhanced adhesive properties have been discovered.
  • the subject coatings are composed of coatings comprising styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene-butylene-styrene (SEBS), or styrene- ethylene-propylene (SEP) block copolymers, aromatic solvents and optionally an adhesion enhancing additive (such as the Dow Inte ⁇ olymer Binder (DIB)).
  • SIB Dow Inte ⁇ olymer Binder
  • Solvents of low volatility maximize the time for polymer chain entanglement between the coating polymer and substrate polymer. Since the substrate polymer was a new composition and not a block copolymer, choice of solvent(s) was unknown and not predictable. Determination of solubility parameter was incorrect in predicting solubility and development of adhesion.
  • the preferred SBS polymers include, but are not limited to, those of 30+/- 5 percent styrene content. Increased styrene content creates harder, less flexible films, but apparently does not affect adhesion. Harder films can be subject to cracking when coated onto flexible substrates.
  • SBS polymers composed of unsaturated midblock monomers, have lower adhesion than polymers of saturated midblock on saturated polymer substrates, such as ethylene-styrene block inte ⁇ olymers (ESIs), especially those of critical surface tension less than 30.
  • the preferred SEBS and SEP polymers include, but are not limited to, those of 30+/-5 percent styrene content. Increased styrene content creates harder, less flexible films, but apparently does not affect adhesion. Harder films can be subject to cracking when coated onto flexible substrates.
  • ESI polymers were also found to be convenient and efficient as coatings polymers for ESI substrates. Being of similar composition, good compatibility with ESI substrates was suspected. However, solubility and high molecular weights of the ESI polymers made practical coatings formulation suspect, though the contrary has now been shown true. Variation of ESI polymer coating (material composition) separate from the substrate material was advantageous to alter gloss and other surface properties in appearance and resistance.
  • the substrate when the substrate was low in styrene content, (for example, ESI inte ⁇ olymers with styrene contents of -30-40 weight percent), and was coated with a coating composition comprising higher styrene content ESI inte ⁇ olymers (with styrene contents of -60-70 wt percent), then gloss was improved from 10 or less units (60° gloss, ASTM D-523) to greater than 70 units relative to the uncoated material. Benefits in surface hardness (scratch or mar resistance) or glove feel (softness) of the surface can also be altered accordingly.
  • styrene content for example, ESI inte ⁇ olymers with styrene contents of -30-40 weight percent
  • a coating composition comprising higher styrene content ESI inte ⁇ olymers (with styrene contents of -60-70 wt percent)
  • gloss was improved from 10 or less units (60° gloss, ASTM D-523)
  • the preferred ESI polymers include, but are not limited to, those of melt index greater than 0.1 but less than 200. Higher melt index allows formulation of higher percent solids coatings at application viscosities for spray or brush. Surface properties can be altered by changing the coating polymer styrene content as noted above. Increased styrene content (>50 percent) creates harder, less flexible films, but apparently does not affect adhesion. Harder films can be subject to cracking when coated onto flexible substrates. However, doping the harder polymers with 5-10phr of softer ESI polymers, no limitations on melt index, dramatically improves low temperature flex cracking properties without significantly affecting scratch resistance or gloss. Dopant, flexible ESI polymers must still be compatible with coating solvents and substrate polymer for optimal formulation viscosity, substrate adhesion, scratch resistance, and gloss.
  • the filler holding capacity of ESI's can be used to create a new, simplified paint or ink manufacturing process.
  • colors are first added to the ESI (via compounding or other melt mixing techniques) and then the resulting pigment containing compound is added directly to the let down solution.
  • This process represent a simplification over the more traditional paint or ink manufacturing processes which add the pigment via a mill base step.
  • the following examples are illustrative of the invention, but are not to be construed as to limiting the scope thereof in any manner.
  • the molecular weight of the polymer compositions for use in the present invention is conveniently indicated using a melt index measurement according to ASTM D-1238, Condition 190°C/2.16 kg (formally known as "Condition (E)” and also known as 12) was determined. Melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear.
  • Also useful for indicating the molecular weight of the substantially random inte ⁇ olymers used in the present invention is the Gottfert melt index (G, cm 3 / 10 min) which is obtained in a similar fashion as for melt index (I 2 ) using the ASTM D1238 procedure for automated plastometers, with the melt density set to 0.7632, the melt density of polyethylene at 190°C.
  • melt density to styrene content for ethylene-styrene inte ⁇ olymers was measured, as a function of total styrene content, at 190°C for a range of 29.8 percent to 81.8 percent by weight styrene. Atactic polystyrene levels in these samples was typically 10 percent or less. The influence of the atactic polystyrene was assumed to be minimal because of the low levels. Also, the melt density of atactic polystyrene and the melt densities of the samples with high total styrene are very similar.
  • the method used to determine the melt density employed a Gottfert melt index machine with a melt density parameter set to 0.7632, and the collection of melt strands as a function of time while the 12 weight was in force. The weight and time for each melt strand was recorded and normalized to yield the mass in grams per 10 minutes. The instrument's calculated I2 melt index value was also recorded. The equation used to calculate the actual melt density is ⁇ - ⁇ 07632 x l2 /l2 Gottfert
  • S weight percentage of styrene in the polymer.
  • S weight percentage of styrene in the polymer.
  • the relationship of total styrene to melt density can be used to determine an actual melt index value, using these equations if the styrene content is known.
  • Inte ⁇ olymer styrene content and atactic polystyrene concentration can be determined using proton nuclear magnetic resonance ( ⁇ N.M.R) or by 13 C nuclear magnetic resonance.
  • TCE-d 2 A 0.75 mL aliquot of TCE-d 2 was added by syringe and the tube was capped with a tight-fitting polyethylene cap. The samples were heated in a water bath at 85°C to soften the inte ⁇ olymer. To provide mixing, the capped samples were occasionally brought to reflux using a heat gun. Proton NMR spectra were accumulated on a Varian VXR 300 with the sample probe at 80°C, and referenced to the residual protons of TCE-d 2 at 5.99 ppm. The delay times were varied between 1 second, and data was collected in triplicate on each sample. The following instrumental conditions were used for analysis of the inte ⁇ olymer samples:
  • VXR-300 standard ⁇ : Sweep Width, 5000 Hz Acquisition Time, 3.002 sec Pulse Width, 8 ⁇ sec Frequency, 300 MHz
  • Integrals were measured around the protons labeled in FIGURE 1 ; the 'A' designates aPS. Integral A 7 , (aromatic, around 7.1 ppm) is believed to be the three ortho/para protons: and integral A 66 (aromatic, around 6.6 ppm) the two meta protons.
  • the two aliphatic protons labeled ⁇ resonate at 1.5 ppm; and the single proton labeled b is at 1.9 ppm.
  • the aliphatic region was integrated from 0.8 to 2.5 ppm and is referred to as A al .
  • the theoretical ratio for A 7 1 : A 66 : A al is 3: 2: 3, or 1.5: 1 : 1.5, and correlated very well with the observed ratios for the StyronTM 680 sample for several delay times of 1 second.
  • the ratio calculations used to check the integration and verify peak assignments were performed by dividing the appropriate integral by the integral A 66 Ratio A. is A 7 , / A 66 .
  • Region A 66 was assigned the value of 1. Ratio Al is integral A a , / A 66 . All spectra collected have the expected 1.5: 1: 1.5 integration ratio of (o+p): m: ( ⁇ +b). The ratio of aromatic to aliphatic protons is 5 to 3. An aliphatic ratio of 2 to 1 is predicted based on the protons labeled ⁇ and b respectively in Figure 1. This ratio was also observed when the two aliphatic peaks were integrated separately.
  • the 'H NMR spectra using a delay time of one second had integrals C 7 ,, C 66 , and C a , defined, such that the integration of the peak at 7.1 ppm included all the aromatic protons of the copolymer as well as the o & p protons of aPS.
  • integration of the aliphatic region C a in the spectrum of the inte ⁇ olymers included aliphatic protons from both the aPS and the inte ⁇ olymer with no clear baseline resolved signal from either polymer.
  • s c and e c are styrene and ethylene proton fractions in the inte ⁇ olymer, respectively, and S c and E are mole fractions of styrene monomer and ethylene monomer in the inte ⁇ olymer, respectively.
  • the total styrene content was also determined by quantitative Fourier Transform Infrared spectroscopy (FTIR). Preparation of Substantially Random Ethylene/Styrene Inte ⁇ olvmers ("ESI's) Used in the Examples of the Present Invention.
  • FTIR Fourier Transform Infrared spectroscopy
  • ESI's 1 -6 were prepared by polymerizing a mixture of ethylene, styrene and hydrogen under solution process conditions in the presence of one or more metallocene or constrained geometry catalysts.
  • the properties of ESI's 1 - 7 are summarized in Table 5.
  • ESI 7 is a melt blend of 75 wt percent ESI 4 and 25wt percent DowlexTM IP 60 (a product and trademark of The Dow Chemical Company.
  • Test parts and characterization data for the inte ⁇ olymers and their blends were generated according to the following procedures:
  • ESI's 1 -7 were molded on a DEMAG Dl 50-275 injection molding machine at a barrel temperature of 160° - 170°C and a mold temperature of 10 - 20°C .
  • the injection time was three seconds and the injection pressure was 2000 psi.
  • a hold time of 15 second and a cooling time of 10 seconds was employed.
  • Percent solids of materials, for coating and substrate polymers, was then measured as a indication of solubility and solvent susceptibility in a given solvent blend. Material was added to the above solvent blends in amounts as shown in Table 8.
  • Polymer material was preweighed into glass vials and solvent pipetted in as a constant volume. Samples were shaken to mix and placed in a 50°C oven. Vials were removed from the oven, the contents manually stirred, and the vials replaced in the oven after 24 hours. Samples were removed from the oven after 48 hours and let stand at room temperature overnight (-15 hours) to equilibrate. [For baked coatings, samples would be equilibrated at the proposed baking temperature, instead of room temperature, until just before weighing.] Aliquots ( ⁇ 1.5g, net weight) were then removed from the clear, supernatant layer of each sample and placed into a preweighed (tare weight) aluminum pan, baked in a forced-air oven at 120°C overnight, cooled, and reweighed.
  • Tape test and rub test values of 4 or greater are considered good adhesion, 2 to 3 marginal, and 1 or less poor adhesion.
  • a rating of 4 or greater for rub adhesion is considered as " durable" or wear resistant adhesion.
  • Adhesion to plastic substrates develops over a one to five day period, proportional to the quantity of high boiling aromatic solvent present. Pigmentation to 12 PVC reduces adhesion by 1-2 adhesion units. Adhesion measured before all high boiling solvent had evaporated demonstrated no adhesion (0) between the substrate and the coating polymer. Adhesion, upon thorough drying, increased with high boiling aromatic solvent content. In the absence of high boiling solvent, clear coatings of 3 adhesion were obtained. Increasing the weight percent of high boiling solvent to 20 percent (relative to total solvent) improved adhesion to 4, while solvent contents above 50 percent relative to the weight of solvent gave durable (5) adhesion.
  • the use of high boiling aromatic solvent increased dry time. Up to three days were required for durable adhesion while block resistance developed within 15 minutes at room temperature. All delamination (tape tests) occurred prior to 3 days drying time, although drying time can be reduced by baking the article at temperatures above ambient with fresh air circulated to the part surface.
  • Gloss values (measured by method ASTM D523) were - 60 for clear coatings with -30 percent solids or higher. Gloss values (measured by method ASTM D523) were - 80 units for clear coatings with -15-20 percent solids. Thus the percent solids of the coating formulation affects gloss.
  • Adhesion to ESI 7 developed over a one to five day period, and was proportional to both the quantity of high boiling solvent present and the relative evaporation rate of the solvent system.
  • Pigmentation to 12 Pigment Volume Concentration (PVC) reduced adhesion by up to 1 - 2 adhesion units.
  • Adhesion measured before all high boiling solvent had evaporated demonstrated no adhesion (0 rating) between the substrate and the coating polymer.
  • Gloss values were - 60 for clear coatings with -30 percent solids or higher. Gloss values (measured by method ASTM D523) were - 80 units for clear coatings with -15-20 percent solids. Percent solids of the coating formulation thus affects gloss. Gloss values were somewhat lower for ESI 3 compared to ESI's 1 and 2, thus higher mole percent ethylene content (or lower mol percent styrene content) in the ESI thus reduces gloss.
  • a coatings was formulated at 17 wt percent ESI 2 solids and 12 pigment volume concentration (PVC) on an ESI 7 substrate, Table 14 describes the millbase and Table 15 describes the letdown.
  • Cyclosol 100 is a trademark standard dispersing resin manufactured by BYK Chemie, a high molecular weight block copolymer resin with pigment affinic groups for use in relatively non-polar media. Compatibility with non- polar media improved dispersion stability and development of coating gloss.
  • CycloSol 100 is a trademark of Shell Chemical Co., consisting of a C 8 + (excluding ethylbenzene) aromatic fraction boiling between 150 and 175°C (300 and 350°F).
  • Cypar 9 is a trademark of Shell Chemical Co., consisting of a C 8 + (excluding ethylbenzene) aromatic fraction boiling between 150 and 175°C (300 and 350°F).
  • the Base Paint was produced by making a paste, a solvent system and a resin system according to Table 16
  • ESI solutions were prepared for the pu ⁇ ose of modifying the base paint. These solutions were prepared by dissolving 10 percent ESI polymer into toluene. The solutions were made in a 1 liter resin kettle, with an air stirrer and a water cooled condenser. Temperature was controlled using an Omron E5EX temperature controller with the thermocouple in the solution. The maximum solution temperature was 108 C. The solution was allowed to heat and stir for 2-3 hr. To ensure complete dissolution of the polymer. The stirrer was turned off, the heating mantel removed, the stirrer turned back on and the solution allowed to cool to room temperature 25 C, taking approximately 3 hours. The ESI's are described in Table 17. Table 17. ESI Solutions Produced
  • the base paint described above was mixed with the ESI solutions from Table 17 and toluene as shown in Table 18.
  • Hardness, gloss, abrasion resistance and low temperature flexibility are generally desirable properties of coatings such as paint.
  • a series of experiments, using coating formulations containing ESI 1 was conducted to determine the effect of several tackifying resins on coating properties such as hardness, gloss, adhesion and low temperature flexibility. These results are compared with coating formulations containing styrenic block copolymers. Compatibility was ascertained by clarity of the polymer and resin solution and of the resultant coating.
  • Table 19 shows gloss measured both before and after (numbers in parentheses) abrasion with white paper.
  • An abrasion test was developed to measure the surface hardness of the polymer coatings. Standard long grain copier paper was used as the abrasive media. The sample was pulled against the grain of the paper 10 cycles while pressing the sample firmly into the paper. Gloss of the abraded sample was compared to the original gloss; less change in gloss indicated a harder, more scratch resistant coating.
  • Low temperature flexibility was measured by placing coated ESI 7 samples in a -5°C freezer for 0.5 hours. Samples were removed and immediately bent through 180°. Microscopic examination at 10 to 60X magnification showed presence/absence of crack defects and extent of failure. Coatings were assigned a pass (no defects) or fail (presence of any cracking due to flex) rating as shown in Table 21. Low temperature flexibility of Kraton containing coatings was unaffected by tackifier type or amount. In the case of ESI 1 containing coatings, low temperature flexibility is decreased in the presence of tackifying resins. This is expected since the hardness of these coatings increases in the presence of these same tackifying resins.
  • Low temperature flexibility can be improved by utilizing a blend of ESI's in the coating formulation.
  • addition of 10 parts ESI 3 per 100 parts ESI 2 makes the microcracks invisible to the naked eye, with further improvements in flex at 20 and 30 phr ES ⁇ .
  • Table 21 Tackifying Resins - Effect on Low Temperature Flexibility*

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  • Paints Or Removers (AREA)
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Abstract

L'invention concerne une formulation de revêtement comprenant: (A) de 0,1 à 100 % en poids (sur la base du poids total de ladite formulation) d'au moins un interpolymère sensiblement aléatoire, renfermant: (1) des unités polymères dérivées de (i) au moins un monomère aromatique de vinyle ou de vinylidène, ou (iv) au moins un monomère aliphatique ou cycloaliphatique de vinyle ou de vinylidène, ou (v) une combinaison d'au moins un monomère aromatique de vinyle et au moins un monomère aliphatique ou cycloaliphatique de vinyle ou de vinylidène; (2) des unités polymères dérivées au moins de l'éthylène et/ou d'une α-oléfine C3-20; et/ou (4) des unités polymères dérivées d'un ou de plusieurs monomères polymérisables éthyléniquement insaturés autres que ceux dérivés de (1) et (2); (B) de 0 à 99,9 % en poids d'une résine supplémentaire (sur la base du poids total de la formulation); (C) de 0 à 99,9 % en poids (sur la base du poids total de la formulation) d'un solvant; et (D) de 0 à 99,9 en poids (sur la base du poids total de la formulation) d'un ou de plusieurs additifs choisis dans le groupe comprenant les liants, les tensioactifs, les diluants, les promoteurs d'adhésion, les charges, les agents gluants et les auxiliaires de traitement, les résines durcissantes, les additifs modificateurs de surface et leurs combinaisons.
PCT/US1999/025826 1998-11-06 1999-11-03 Compositions de revetement contenant des interpolymeres aromatiques d'alpha-olefine/vinyle ou vinylidene et/ou des interpolymeres aliphatiques ou cycloaliphatiques de vinyle ou de vinylidene steriquement encombres WO2000027936A1 (fr)

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AU17117/00A AU1711700A (en) 1998-11-06 1999-11-03 Coatings compositions containing alpha-olefin/vinyl or vinylidene aromatic and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers
JP2000581106A JP2002529573A (ja) 1998-11-06 1999-11-03 α−オレフィン／ビニルもしくはビニリデン芳香族及び／又はヒンダード脂肪族もしくは脂環式ビニルもしくはビニリデンインターポリマーを含有するコーティング組成物

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0478800A1 (fr) * 1990-04-18 1992-04-08 Mitsui Petrochemical Industries, Ltd. Colle fusible
WO1998010017A1 (fr) * 1996-09-04 1998-03-12 The Dow Chemical Company Compositions a copolymere sensiblement statistique d'au moins une alpha-olefine et avec au moins un monomere vinylidene aromatique ou vinylidene aliphatique empeche
JPH1087743A (ja) * 1996-09-18 1998-04-07 Mitsui Petrochem Ind Ltd 電気絶縁体用エチレン・芳香族ビニル化合物共重合体、電気絶縁体用組成物、これらからなる電線用被覆材および電線
WO1999019398A1 (fr) * 1997-10-15 1999-04-22 The Dow Chemical Company COMPOSITIONS THERMOPLASTIQUES D'INTERPOLYMERES DE MONOMERES D'α-OLEFINES AVEC UN OU PLUSIEURS MONOMERES VINYLIQUES OU VINYLIDENE AROMATIQUES ET/OU UN OU PLUSIEURS MONOMERES VINYLIQUES OU VINYLYDENE ALIPHATIQUES OU CYCLOALIPHATIQUES ENTRAVES MELANGES A DES HOMOPOLYMERES ET DES COPOLYMERES D'HALOGENURE DE VINYLE
WO1999020685A1 (fr) * 1997-10-17 1999-04-29 The Dow Chemical Company Compositions d'interpolymeres de monomeres d'alpha-olefine un ou plusieurs monomeres aromatiques de vinyle ou de vinylidene
WO1999024492A1 (fr) * 1997-11-12 1999-05-20 The Dow Chemical Company Dispersions ou emulsions aqueuses d'interpolymeres d'alpha-olefine(s)/monomere(s) aromatique(s) de vinylidene entrave

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0478800A1 (fr) * 1990-04-18 1992-04-08 Mitsui Petrochemical Industries, Ltd. Colle fusible
WO1998010017A1 (fr) * 1996-09-04 1998-03-12 The Dow Chemical Company Compositions a copolymere sensiblement statistique d'au moins une alpha-olefine et avec au moins un monomere vinylidene aromatique ou vinylidene aliphatique empeche
JPH1087743A (ja) * 1996-09-18 1998-04-07 Mitsui Petrochem Ind Ltd 電気絶縁体用エチレン・芳香族ビニル化合物共重合体、電気絶縁体用組成物、これらからなる電線用被覆材および電線
WO1999019398A1 (fr) * 1997-10-15 1999-04-22 The Dow Chemical Company COMPOSITIONS THERMOPLASTIQUES D'INTERPOLYMERES DE MONOMERES D'α-OLEFINES AVEC UN OU PLUSIEURS MONOMERES VINYLIQUES OU VINYLIDENE AROMATIQUES ET/OU UN OU PLUSIEURS MONOMERES VINYLIQUES OU VINYLYDENE ALIPHATIQUES OU CYCLOALIPHATIQUES ENTRAVES MELANGES A DES HOMOPOLYMERES ET DES COPOLYMERES D'HALOGENURE DE VINYLE
WO1999020685A1 (fr) * 1997-10-17 1999-04-29 The Dow Chemical Company Compositions d'interpolymeres de monomeres d'alpha-olefine un ou plusieurs monomeres aromatiques de vinyle ou de vinylidene
WO1999024492A1 (fr) * 1997-11-12 1999-05-20 The Dow Chemical Company Dispersions ou emulsions aqueuses d'interpolymeres d'alpha-olefine(s)/monomere(s) aromatique(s) de vinylidene entrave

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Title
CHEMICAL ABSTRACTS, vol. 128, no. 23, 8 June 1998, Columbus, Ohio, US; abstract no. 283690, XP002133819 *

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