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WO2010049320A1 - Procédé permettant de modifier le brillant avec des dérivés de mélanine et des produits connexes et utilisations - Google Patents

Procédé permettant de modifier le brillant avec des dérivés de mélanine et des produits connexes et utilisations Download PDF

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Publication number
WO2010049320A1
WO2010049320A1 PCT/EP2009/063766 EP2009063766W WO2010049320A1 WO 2010049320 A1 WO2010049320 A1 WO 2010049320A1 EP 2009063766 W EP2009063766 W EP 2009063766W WO 2010049320 A1 WO2010049320 A1 WO 2010049320A1
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WIPO (PCT)
Prior art keywords
styrene
copolymer
polymer
polyamide
ethylene
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PCT/EP2009/063766
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English (en)
Inventor
Martin Brunner
Gregor Huber
Isabelle Rapenne-Jacob
Laurent Simonpietri
Michael Tinkl
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts

Definitions

  • the invention relates to the use of melamine derivatives as gloss modifiers in polymer products and to corresponding methods and processes, as well as obtainable products.
  • the present invention also provides a method of modulating, especially reducing the gloss of polymeric compositions comprising adding melamine derivatives to polymeric compositions, methods for their manufacture and the corresponding polymeric compositions, as well as products made from these polymeric compositions.
  • Low gloss polymeric compositions formed in accordance with the present invention are suitable for applications where the use of polymers having a matte surface finish is advantageous such as, for example, some automotive (interior) applications.
  • Advanced materials based on PP continue to be popular for automotive interior and exterior components due to major advantages such as low density, convenient processability and good cost/performance balance.
  • the final customers (especially car buyers) continue to increase their quality demands.
  • the (especially car) manufacturers try to meet these demands through improved surface properties, such as scratch resistance, styling harmony, new co- lours and valuable look, as well as good safety properties, e.g. avoiding disturbing light reflections.
  • the highest level of interest for interior applications are seen in instrument panel structures, consoles, other interior trim parts, instrument panels as such and door panel skins, but also seat components, handles, cargo liners, engine compartment components or the like. Also in other fields corresponding materials are of interest, e.g. for machine housings, appliances, consumer or electronic devices, outdoor vehicles and devices or any other parts or (e.g. fibre or film) articles needing good mechanical strength and favourable optics, such as low gloss.
  • the main substrates, for which low gloss and improved scratch resistance remain an unrealized need are substrates like talc-filled PP copolymer or PP based TPE (skin).
  • composition of these materials can vary in a wide range, it is clear, that low gloss and scratch resistance depends on the resin used, the type and content of elastomer and talc, stabilizers and co-additives as well as pigments and other fillers. In addition also the processing conditions and the surface texture (grain) play an important role.
  • These new materials are intended to be used without any coatings and may be used for both positive (grained during skin fabrication) and negative (grained in the mould tooling) forming process.
  • compositions that allow for the manufacture of products as mentioned without requiring additional coatings or surface treatments.
  • compositions allowing with low gloss properties while maintaining other important properties such as scratch resistance and mechanical properties, e.g. tensile modulus, tensile stress at break, tensile strain at break and impact resistance .
  • Low gloss surfaces of the automotive interior are needed especially for two reasons: a) Safety, e.g. lower reflection from the dashboard on to the windshield, b) Design and aesthetics: low gloss surfaces are perceived as higher quality and higher value parts.
  • the main substrates meaning basis materials for articles), for which low gloss and improved scratch resistance remain an unrealized need, are substrates like talc-filled PP copolymer or PP based TPE (skin).
  • substrates like talc-filled PP copolymer or PP based TPE (skin).
  • talc-filled PP copolymer or PP based TPE (skin).
  • PP based TPE skin
  • the composition of these materials can vary in a wide range, it is clear that low gloss and scratch resistance depends on the resin used, the type and content of elastomer and talc, stabilizers and co-additives as well as pigments and other fillers.
  • the processing conditions and the surface texture (grain) play an important role.
  • These new materials are intended to be used (at least preferably) without any coatings and may be used for both positive (grained during skin fabrication) and negative (grained in the mould tool) forming process.
  • the present invention thus, in a first aspect, provides a method of modulating, especially reducing the gloss of polymeric compositions.
  • Low gloss polymeric compositions formed in accordance with the present invention are suitable for applications where the use of polymers having a matte surface finish is advantageous such as, for example, some automotive (interior) applications.
  • the polymeric compositions formed in accordance with the present invention exhibit improved (especially low) gloss characteristics and good or even improved physical properties.
  • the low gloss compositions are formed by melt mixing of polypropylene - A -
  • compositions with the melamine additives according to the invention are provided.
  • Fillers such as talc and wollastonite and other processing additives may also be included in the compositions according to the invention.
  • Other customary additives in the polymer field may be present as well.
  • the present invention thus especially includes a method or process for modulating, especially reducing (lowering), the gloss of a polymer article (the term article including herein a flat product such as a film or a skin, or a three-dimensional product) and/or for producing a low gloss polymer article, comprising adding (especially by melt mixing) to the bulk starting polymer mixture a melamine derivative to modulate, especially reduce (lower), the gloss (in comparison to an otherwise identical mixture which, however, lacks the addition of the melamine derivative) and then forming the article, or the use of a melamine derivative as additive to reduce gloss of a polymer article by adding it to the mixture used for forming said polymer article.
  • an amount of melamine derivative is added that is effective in lowering the gloss in comparison to the composition lacking said melamine derivative (but which is otherwise identical).
  • the conditions of the manufacture of the polymer article to be produced are chosen so that the melamine derivative addition, especially the amount and/or the type of the melamine derivative, in combination with the chosen process conditions leads to a lowering of gloss compared to an article that has an otherwise identical composition but that lacks the melamine derivative(s).
  • moduleating the gloss is used in the present specification, this is also intended to mean that the gloss may be adapted to a desired value, that is, in principle it is also possible that the gloss is increased. In one embodiment of all invention embodiments described herein, the term is however especially used for "reducing" (lowering) the gloss.
  • thermoplastic resin composition according to the present invention can be formed into a variety of articles by known methods such as thermoforming, extrusion, processing of fibrous substrates, sheet forming, or especially moulding, e.g. extrusion moulding, vacuum moulding, profile moulding, foam moulding, injection moulding, blow moulding, compression moulding, rotational moulding, or the like.
  • moulding e.g. extrusion moulding, vacuum moulding, profile moulding, foam moulding, injection moulding, blow moulding, compression moulding, rotational moulding, or the like.
  • the present invention also relates to the use of a melamine derivative as gloss diminishing agent, whereby the melamine derivative is added to a mixture used for forming a polymer article.
  • indefinite article “a” or “an” is used, this is intended to include “at least one”, e.g. “one or more”, where “the” is used referring to a feature with an indefinite article, this is also intended to mean “at least one”.
  • the polymeric compositions formed in accordance with the present invention exhibit improved low gloss characteristics and improved physical properties.
  • the low gloss compositions are formed conveniently by melt mixing of the polymer substrate, such as polypropylene compositions, with the additives covered in this invention.
  • the present invention relates to especially commercially available flame retardants products Melamine cyanurate (MELAPUR MC) and Melamine polyphosphate (MELAPUR 200). These products are described according to the invention to be useful and used as surface modifier, especially as low gloss additives in PP/TPO polymer compositions and products for automotive applications.
  • Melamine cyanurate MELAPUR MC
  • Melamine polyphosphate MELAPUR 200
  • the 1 ,3,5-triazine compound melamine can be described in chemical terms as 2,4,6- triamine-1 ,3,5-triazine. Many derivatives are known, e.g. melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, diamine phenyltriazine or the like.
  • melamine cyanurate is preferred, which may be described in general e.g. by the following summarizing formula:
  • At least part of the melamine composition e.g. at least 10 %, e.g. at least 20 %, e.g. at least 30%, e.g. at least 40%, e.g. at least 50%, e.g. at least 60%, e.g. at least 70%, e.g. at least 90% by weight, respectively, of the melamine derivative composition can be of the summarizing formula shown above.
  • a melamine derivative according to the invention preferably comprises a structure that, in simplified form, may be characterized by the following formula:
  • This formula merely serves for illustrating structural features that may be comprised in the composition without providing a limiting structure of the whole composition, especially illustrating how the molecules comprised may interact in a small sector of a melamine cyanurate composition useful according to the invention.
  • Ciba MELAPUR® MC Ciba, Basel, Switzerland
  • the melamine cyanurates can be manufactured according to methods that are known in the art, e.g. as described in WO 03/035736 or especially US 5,202,438, each of which is commonly accessible and incorporated by reference herein especially regarding the general and exemplary manufacturing methods and the products described therein.
  • melamine phosphates are to be mentioned. These can be described by the following summary formula:
  • melamine monophosphate 1
  • melamine pyrophosphate 2
  • melamine polyphosphates 3 or larger
  • This type of composition is usually also referred to as melamine polyphosphate.
  • melamine (poly)phosphate is the corresponding composition known under the CAS Nr.: 218768-84-4, especially represented by the commercial name Ciba MELAPUR® 200 (Ciba, Basel, Switzerland).
  • the melamine phosphates can be manufactured according to methods that are known in the art, e.g. as described in WO 00/02869 which is commonly accessible and incorporated by reference herein especially regarding the general and exemplary manufacturing methods and the products described therein.
  • products comprising co-polyphosphates, 1 ,3,5-triazine building blocks and ammonium building blocks, e.g. as described in WO 03/031417 which is commonly available and, especially regarding the compounds of the formula I therein and their manufacture, is incorporated by reference here.
  • composition used for forming an article according to the invention preferably comprises the melamine derivative in an amount (by weight) of 0.2 to 40 %, more preferably from about 2 to about 30 % or preferably to about 25 %, yet more preferably from about 2 to about 18 %, e.g. from about 5 to about 15 % by weight.
  • the size of the melamine derivative particles can e.g. be in the range from about 0.1 to about 100 ⁇ m, e.g. from about 0.2 ⁇ m to about 50 ⁇ m, such as from about 0.5 ⁇ m to about 30 ⁇ m (mean size as measured e.g. by electron microscopy or preferably by laser diffraction - preferably the size distribution is such that more than 50, more preferably more than 75 % of the particles (by weight) are within ⁇ 50 % of the mean value. Most preferably the numbers mentioned above refer to the d50 particle size obtained according to or in analogy to ISO 13320-1.
  • an amount of melamine derivative is added that is effective in lowering the gloss is mentioned, this is especially meant to include an amount that leads to a reduction of gloss of the resulting article when compared with the otherwise identical composition of an article without added melamine derivative, e.g. (using the method given in the Examples) to a lowering of the gloss by 2 % or more, e.g. by 5% or more, for example by 10 to 99%.
  • the process conditions in the methods or uses according to the invention may be modified so as to allow the reduction of gloss in comparison to conditions where no reduction of gloss is possible.
  • the parameters that may be modulated are, e.g., the temperature of the melting, the rate of moving the material into the device forming the desired product (e.g. a form for moulding, an extruder, nozzles or the like), the temperature for filling a form for moulding (especially the temperature of the mould before introduction), the temperature of the forming device, the temperature of the processing to the solid product, and the like.
  • the temperature of the mould can be selected in the range from about 20 to about 60 0 C, e.g. in the range from 20 to 30 0 C
  • the temperature of injection can preferably be chosen in the range from 200 to 280 0 C, e.g. in the range from 200 to 230 0 C
  • the injection speed under the equipment conditions given in the Examples can preferably be chosen in the range from 5 mm/sec to 120 mm/sec, e.g. from about 10 to about 100 mm/sec, at least as a starting point if a further experiment should be required.
  • the basis material (polymer substrate) for the compositions useful for the low gloss products according to the invention may be selected from any type of polymers or polymer mixtures appropriate for melt mixing.
  • a styrene comprising polymer such as ABS (acrylonitrile-butadiene-styrene polymers), SBS (styrene-butadiene-styrene triblock copolymers), SAN (styrene-acrylonitrile copolymers), ASA (acrylonitrile-acrylate elastomer-styrene copolymers, also acrylonitrile- styrene-acrylate), a polyester, for example derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones such as such as PBT (poly(butylene terephthalate), PET (poly(ethylene terephthalate), poly-1 ,4-
  • polyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams such as polyamide 4, polyamide 6, polyamides 6/6, 6/10, 6/9, 6/12, 4/6, 66/6, 6/66, polyamide 11 , polyamide 12, partially aromatic (co)polyamides, for example polyamides based on an aromatic diamine and adipic acid, polyamides prepared from an alkylene diamine and iso- and/r terephthalic acid and copolyamides thereof, copolyether amides, copolyester amides and the like), TPU (thermoplastic elastomers on urethane basis), PS (poly(styrene)), HIPS (high impact poly(styrene)), PC (polycarbonates), as poly(aromatic carbonate)s or poly(aliphatic carbonate)s, e.g.
  • PC/ABS polycarbonate/acrylonitrile-butadiene-styrene blend
  • ABS/PBT acrylonitrile-butadiene- styrene/poly(butylenes terephthalate) blend
  • PVC polyvinyl chloride
  • PVC/ABS polyvinyl chlorideyacrylonitrile-butadiene-styrene polymer
  • PVC/ASA polyvinyl chlorideyacrylonbitrile-styrene-acrylate
  • PVC/acrylate acrylate-modified PVC
  • ionomers copolymerisates of an ionized (at least partially) and an electrically neutral monomer.
  • the polymer substrate is a polyolefin (e.g. High Crystalline PP), PC/ABS, ABS, a polyamide, such as PA-6, or a polyolefin rubber or TPE, or for example a polymer as mentioned specifically in the Examples.
  • polyolefins are: Polymers of monoolefins and diolefins, e.g. polypropylene, e.g. High Crystalline polypropylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, e.g. cyclopenten or norbornene, polyethylene (optionally crosslinked), e.g.
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW medium density polyethylene
  • MDPE low density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE and ULDPE or mixtures of two or more of the polymers just mentioned, e.g. mixtures of polypropylene with polyisobutylene, with polyethylene (for example PP/HDPE or PP/LDPE) or mixtures of different types of polyethylene (e.g.
  • LDPE/HDPE low density polyethylene
  • copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1- ene copolymers, ethylene/hexane copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene /alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide, as well as er
  • Thermoplastic elastomers comprise e.g. rubber modified polyolefins are also known as thermoplastic polyolefins (TPO). They are basically blends of the polymers mentioned above as polyolefins with impact modifiers, such as ethylene-propylene-diene monomer copolymers (EPDM), copolymers of ethylene with higher alpha-olefins (such as ethylene-octene copolymers), polbutadiene, polyisoprene, styrene-butadiene copolymers, hydrogenated styrene-butadiene copolymers, styrene-isoprene copolymers, hydrogenated styrene-isoprene copolymers and the like.
  • EPDM ethylene-propylene-diene monomer copolymers
  • copolymers of ethylene with higher alpha-olefins such as ethylene-octene copolymers
  • TPOs thermoplasctic polyolefins
  • an appropriate TPO has from about 10 to about 90 weight percent of propylene homopolymer, copolymer or terpolymer, and about 90 to about 10 weight percent of an elastic copolymer of ethylene and a C 3 -C 8 -alpha-olefin.
  • Polyolefins and rubber modified polyolefins may not solely be the polymer substrate of the present compositions. Not excluded as polymer substrates are copolymers of polyolefins with other polymers or blends of polyolefins with other polymers as described above.
  • additives can be present in the polymer compositions with regard to the invention.
  • the polymer compositions (polymer substrates) of the present invention thus optionally contain from about 0.01 to about 5%, preferably from about 0.025 to about 2%, and especially from about 0.1 to about 1 % by weight of various further additives, such as the compounds listed below, and optionally in addition up to 40 %, e.g. 0 to 35, for example 10 to 25 % of a nucleating agent or filler (such as talcum), or mixtures thereof:
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol]-2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydroquinones and alkylated hvdroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydr- oxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,21-methylenebis(4-methyl-6-cyclohexylphenol)l 2,2'-methylenebis(6-nonyl-4- methyl phenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -di
  • Benzyl compounds for example 3,5,3 ' ,5,-tetra-tert-butyl-4-4'-dihydroxydibenzyl ether.
  • Hydroxybenzylated malonates for example 3,5,3 ' ,5,-tetra-tert-butyl-4-4'-dihydroxydibenzyl ether.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hydroxyanilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)- 1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris-(3,5-di-tert-butyl-4- hydroxybenzyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)isocyanurate,
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl- ⁇ -tert-butyW-hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1.12. Acylaminophenols. 1.13. Esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols.
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly hydric alcohols 1.14. Esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly hydric alcohols.
  • esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols 1.15. Esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols.
  • esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alco hols 1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alco hols.
  • 2-Hvdroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2'J41-tri hydroxy and 2l-hydroxy-4,4'-dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids as for example 4-tert- butyl phenyl salicylate, phenyl salicylate, octyl phenyl salicylate, dibenzoyl resorcinol, bis(4-tert- butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxybenzoate, hexadecyl-S.S-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl- 4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.
  • Nickel compounds for example nickel complexes of 2,2'-thio-bis-[4-(1 ,1 ,3,3-tetrame- thylbutyl)phenol], nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, nickel complexes of ketoximes, or nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • Stericallv hindered amine stabilizers for example 4-hydroxy-2,2,6,6-tetramethylpiperi- dine, 1 -allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1 -benzy-4-hydroxy-2,2,6,6-tetramethyl- piperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetrameth- yl-4-piperidyl) sebacate, bis(1 ,2,2,6,6-pentamethy-4-piperidyl) n-butyl-3,5-di-tert-butyl-4- hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2
  • the sterically hindered amine may also be one of the compounds described in U.S. Pat. No. 5,980,783, the relevant parts of which are hereby incorporated by reference, that is com pounds of component l-a), l-b), l-c), l-d), l-e), l-f), l-g), l-h), l-i), l-j), l-k) or l-l), in particular the light stabilizer 1-a-1 , 1-a-2, 1-b-1 , 1-C-1 , 1-C-2, 1-d-1 , 1-d-2, 1-d-3, 1-e-1 , l-f-1 , 1-g-1 , 1-g-2 or 1-k-1 listed on columns 64-72 of said U.S.
  • the sterically hindered amine may also be one of the compounds described in U.S. Pat. Nos. 6,046,304 and 6,297,299, the disclosures of which are hereby incorporated by reference, for example compounds as described in claims 10 or 38 or in Examples 1-12 or D-1 to D-5 therein.
  • Sterically hindered amines substituted on the N-atom by a hydroxy-substituted alkoxy group for example compounds such as 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy- 2,2,6,6-tetramethylpiperidine, 1 -(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6- tetramethylpiperidine, the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine with a carbon radical from t-amylalcohol, 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2, 2,6,6- tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1 -(2- hydroxy-(2-
  • Tris-aryl-o-hydroxyphenyl-s-triazines for example known commercial tris-aryl-o-hydroxy- phenyl-s-triazines and triazines as disclosed in, U.S. Patent Nos.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonyl phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, di
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium
  • Nucleating agents for example inorganic substances such as talcum, metal oxides such as titanium dioxide, magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides such as titanium dioxide, magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (ionomers).
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • Dispersing Agents such as polyethylene oxide waxes or mineral oil.
  • additives for example plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, rheology additives, catalysts, flow-control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke inhibitors, flameproofing agents, antistatic agents, clarifiers such as substituted and unsubstituted bisbenzylidene sorbitols, benzoxazinone UV absorbers such as 2,2'-p-phenylene-bis(3,1-benzoxazin-4-one), Cyasorb® 3638 (CAS# 18600-59-4), and/or blowing agents.
  • plasticizers for example plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, rheology additives, catalysts, flow-control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke inhibitors, flameproofing agents, antistatic agents, clar
  • additives selected from the group consisting of hindered amine light (especially UV) stabilizers, hindered phenols, phosphites, benzofuranone stabilizers and hydroxyphenylbenzotriazole, hydroxyphenyl-s-triazine or benzophenone ultraviolet light absorbers, fillers or nucleating agents, such as talcum and carbon black, and basic co-stabilizers, such as calcium stearate, or mixtures of two or more thereof.
  • hindered amine light especially UV
  • hindered phenols hindered phenols, phosphites
  • benzofuranone stabilizers and hydroxyphenylbenzotriazole hydroxyphenyl-s-triazine or benzophenone ultraviolet light absorbers
  • fillers or nucleating agents such as talcum and carbon black
  • basic co-stabilizers such as calcium stearate, or mixtures of two or more thereof.
  • Another embodiment of this invention is the use of one or more melamine derivatives as scratch resistance improving agent(s) in polymer composition products as herein described.
  • compositions according to the present invention are also useful for other potential markets besides the (though preferred) automotive applications, e.g. for panel structures, consoles, other interior trim parts, instrument panels as such and door panel skins, but also seat components, handles, cargo liners, engine compartment components or the like, are e.g. for machine housings, appliances, consumer or electronic devices, outdoor vehicles and devices or any other parts needing good mechanical strength and favourable optics, such as low gloss, or in the appliances and packaging markets.
  • the gloss is measured at 60°, additionally also at 20° or 85°, according to ISO 2813 using a Zehntner ZGM 1 120 trigloss Glossmeter (Zehntner GmbH Testing Instruments, Sissach, Switzerland).
  • the scratch resistance is evaluated by measuring the color difference ( ⁇ L value) by means of a spectral photometer Spectraflash SF 600 plus (Datacolor AG, Dietlikon, Switzerland). This measurement corresponds to the difference in brightness of the scratched versus the unscratched polymer surface.
  • the scratches are made with the Scratch Hardness Tester 430 P (Erichsen GmbH & Co. KG, Hemer, Germany)) similar to GME 60280 (a scratch resistance test according to General Motors Europe Engineering Standard GME 60280, Issue 2, July 2004). with a metal tip of 1 mm diameter (cylindrical hard metal pen with ball-shaped end) and a load of 10 N at room temperature.
  • the tensile properties are measured according to ISO 527 using a Zwick Z010 universal testing machine (Zwick GmbH & Co. KG, UIm, Germany) with crosshead speed of 100 mm/min. At least 5 samples are tested for each formulation and average values are calculated. Tensile modulus [MPa], tensile stress at break [MPa] and tensile strain at break [%] are reported.
  • the flexural properties are measure according to ISO 178 again using a Zwick Z010 universal testing machine. At least 5 samples are tested for each formulation and average values are calculated. Flexural modulus [MPa] and flexural strength [MPa] are reported.
  • the determination of the Charpy impact energy is performed according to ISO 179/1 eA using a Zwick 51 13 pendulum impact tester (Zwick GmbH & Co. KG, UIm, Germany).
  • the work of the hammer is 4 J. Samples are notched prior to the impact test, notch with 0.25 mm radius.
  • Example 1 Processing of injection-moulded plaques with TPO (Borealis Daplen ED 012AE) comprising Melamine cvanurate (MELAPUR MC) or Melamine polyphosphate (MELAPUR 200)
  • TPO Borealis Daplen ED 012AE
  • MELAPUR MC Melamine cvanurate
  • MELAPUR 200 Melamine polyphosphate
  • MELAPUR MC or MELAPUR 200 are incorporated in TPO injection moulded plaques according to the following procedure:
  • Daplen ED012AE (Borealis AG, Vienna, Austria) in powder form is mixed together with 20% talc (Luzenac A-20; Rio Tinto, Luzenac Europe, mecanic, France), 2.5% of a carbon black masterbatch, 0.05% calcium-stearate, 0.05% IRGANOX B215 (synergistic antioxidant mixture of a phosphite (— tris(2,4-di-(tert)-butyl-phenyl)phosphite and a hindered phenol (tetrakis-(methylene-(3,5-di-(tertt)-butyl-4-hydrocinnamate))methane, Ciba, Basel, Switzerland), 0.2% TINUVIN 791 FB (UV stabilisator blend of a high and a low molecular weight HALS for synergistic performance in thick section, Ciba, Basel, Switzerland) and 5 or 10% of the melamine cyanurate or the melamine poly
  • the formulations are mixed in a high speed mixer Mixaco Lab CM 12 (Mixaco, Dr. Herfeld GmbH & Co. KG Maschinenfabrik, Neuenrade, Germany) and compounded at 220 0 C to pellets in a twin-screw extruder, e.g. Berstorff ZE 25x33D (KraussMaffei Berstorff GmbH, Hannover, Germany).
  • the pellets are further injection moulded to plaques with a thickness of 2 mm using a standard injection moulding machine, e.g. Engel HL60 (Engel Austria GmbH, Schwertberg, Austria).
  • the processing temperature is around 240 0 C.
  • the average particle size is 2.5 ⁇ m.
  • the gloss is reduced by adding the additives without a substantial change of the scratch resistance and the mechanical properties.
  • Example 2 Processing of injection-moulded plaques with TPO (Borealis Daplen ED 012AE) comprising Melamine cvanurate (MELAPUR MC) or Melamine polyphosphate (MELAPUR 200) - variation of the processing conditions
  • the formulations are prepared as described in example 1 , but the processing conditions during the injection moulding are varied.
  • the injection temperature, the injection speed and the temperature of the mould are varied as follows
  • Table 3 shows the gloss at 85 °.
  • Table 4 shows the scratch resistance ⁇ L at 1 ON:
  • Example 3 Processing of injection-moulded plaques with TPO (Borealis Daplen ED 012AE) comprising Melamine polyphosphate (MELAPUR 200)
  • a minimum in the 60° gloss can be reached in the range of 10% of melamine derivative &.
  • the gloss is increased again.
  • Total amount of talc and melamine derivative 4- is in the best case in the range of 30%.
  • Example 4 Processing of injection-moulded plaques with TPO (Borealis Daplen ED 012AE) comprising Melamine polyphosphate (MELAPUR 200) without talc addition
  • Example 5 Processing of injection-moulded plaques with TPO (Borealis Daplen ED 012AE) comprising Melamine polyphosphate (MELAPUR 200) and scratch resistance additive IRGASURF SR 100
  • the formulations are prepared as described in example 1 . Additionally, 2.5% of a scratch resistance additive IRGASURF SR 100 (Ciba, Basel, Switzerland) is added to the formulations. The experimental results are shown in Table 7.
  • Example 6 Processing of injection-moulded plaques with HCPP (Sabic PP CX02-81 )
  • Example 7 Processing of injection-moulded plaques with PC/ABS (Dow Pulse A35-105)
  • Example 8 Processing of injection-moulded plaques with ABS (Dow Magnum 3504)
  • Example 9 Processing of injection-moulded plaques with TPE (Kraiburg STP 9363 / 33 B 102),
  • Example 10 Processing of fibers with PA-6 (Ultramid BS 700)
  • Formulations of polyamide-6 (Ultramid BS 700 from BASF SE, Ludwigshafen, Germany) are mixed in a high speed mixer Mixaco Lab CM 12 (Mixaco, Dr. Herfeld GmbH & Co. KG Maschinenfabrik, Neuenrade, Germany) turbo mixer and extruded in a twin-screw extruder, (Haake-Poly-Lab extruder from Thermo Fisher Scientific Inc., Düsseldorf, Germany) at 240 0 C. The polymer string is then granulated. The pellets obtained are dried overnight at 80° C. in a vacuum drying oven.
  • the pellets are then processed through a fiber extruder Spinboy Il (Busschaert Engineering, Deerlijk (Belgium) to produce fibers of Denier 10.0.
  • the gloss values of the fibers are then measured by wrapping the fibers around a mirror. For results see Table 12.

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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)

Abstract

La présente invention concerne des procédés permettant de moduler le brillant de matériaux plastiques et les produits fabriqués à partir d'eux, tels que des articles dans l'industrie automobile par ex. destinés à l'intérieur des automobiles, et également l'utilisation de certains additifs à cette fin et les modes de réalisation de l'invention associés. La modulation comprend l'ajout d'un dérivé de mélamine, en particulier un phosphate de mélamine ou un cyanurate de mélamine ou des mélanges de ces composés, à une composition polymère utilisée comme substrat polymère pour les articles.
PCT/EP2009/063766 2008-10-31 2009-10-21 Procédé permettant de modifier le brillant avec des dérivés de mélanine et des produits connexes et utilisations Ceased WO2010049320A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109734982A (zh) * 2018-12-21 2019-05-10 上海高分子功能材料研究所 一种高密度耐低温聚乙烯材料及其制备方法
CN116265554A (zh) * 2021-12-17 2023-06-20 阿特斯阳光电力集团股份有限公司 一种光伏封装材料及其制备方法和应用

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GB1366474A (en) * 1972-02-16 1974-09-11 Cabot Corp Flatted compositions
US4007142A (en) * 1974-04-24 1977-02-08 Balm Paints Limited Amine resin and process
US4228055A (en) * 1978-09-06 1980-10-14 Ppg Industries, Inc. Aqueous coating compositions containing flatting agents and low molecular weight polyethers
WO1997000296A1 (fr) * 1995-06-16 1997-01-03 Dsm N.V. Revetement de poudre mate
US20080241529A1 (en) * 2007-03-29 2008-10-02 Clariant International Ltd. Flameproofed adhesive and sealing materials

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Publication number Priority date Publication date Assignee Title
GB1366474A (en) * 1972-02-16 1974-09-11 Cabot Corp Flatted compositions
US4007142A (en) * 1974-04-24 1977-02-08 Balm Paints Limited Amine resin and process
US4228055A (en) * 1978-09-06 1980-10-14 Ppg Industries, Inc. Aqueous coating compositions containing flatting agents and low molecular weight polyethers
WO1997000296A1 (fr) * 1995-06-16 1997-01-03 Dsm N.V. Revetement de poudre mate
US20080241529A1 (en) * 2007-03-29 2008-10-02 Clariant International Ltd. Flameproofed adhesive and sealing materials

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109734982A (zh) * 2018-12-21 2019-05-10 上海高分子功能材料研究所 一种高密度耐低温聚乙烯材料及其制备方法
CN109734982B (zh) * 2018-12-21 2021-05-28 上海高分子功能材料研究所 一种高密度耐低温聚乙烯材料及其制备方法
CN116265554A (zh) * 2021-12-17 2023-06-20 阿特斯阳光电力集团股份有限公司 一种光伏封装材料及其制备方法和应用

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