WO2020084112A1 - Polymeric composition comprising colorants, its process of preparation, use and object comprising it - Google Patents

Polymeric composition comprising colorants, its process of preparation, use and object comprising it Download PDF

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Publication number
WO2020084112A1
WO2020084112A1 PCT/EP2019/079167 EP2019079167W WO2020084112A1 WO 2020084112 A1 WO2020084112 A1 WO 2020084112A1 EP 2019079167 W EP2019079167 W EP 2019079167W WO 2020084112 A1 WO2020084112 A1 WO 2020084112A1
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Prior art keywords
polymeric composition
colorants
composition pci
polymeric
cai
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PCT/EP2019/079167
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French (fr)
Inventor
Jean-Marc Boutillier
Benoît ANDRE
Sylvain QUERUEL
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Arkema France
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Application filed by Arkema France filed Critical Arkema France
Priority to EP19795171.8A priority Critical patent/EP3870647A1/en
Publication of WO2020084112A1 publication Critical patent/WO2020084112A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/205—Neutral density filters
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers

Definitions

  • Polymeric composition comprising colorants, its process of preparation, use and object comprising it
  • the present invention relates to a polymeric composition
  • a polymeric composition comprising a polymeric elastomeric phase, polymeric particles and a colorants.
  • the present invention relates to a polymeric composition
  • a polymeric composition comprising a polymeric elastomeric phase polymeric particles and a colorants, its process of preparation and use.
  • the present invention concerns also objects or articles comprising a polymeric composition comprising a polymeric elastomeric phase polymeric particles and a colorants.
  • the present invention concerns as well a lightning or luminous device comprising a polymeric composition comprising a polymeric elastomeric phase polymeric particles and a colorants.
  • Thermoplastic polymers and especially (meth) acrylic polymers are widely used, including lightning applications. This is mainly due to its characteristics as a highly transparent polymer material with excellent resistance to ultraviolet radiation and weathering. So (meth) acrylic polymers are used for example in lamps, luminaires, light covers, displays, lit shelving, surfaces and illuminated signs.
  • the lightning applications have various requests on the (meth) acrylic polymers or the compositions based on (meth) acrylic polymers as light transmission, diffusing power.
  • These compositions based on (meth) acrylic polymers comprise generally more or less spherical particles, which are also polymeric particles or other organic particles or inorganic particles.
  • This compromise is based on the correct or optimal quantity of the respective particles in the polymeric composition and colorants in the polymeric composition.
  • the objective of the present invention is to provide a polymeric composition comprising polymeric particles and colorants suitable for lightning applications and having an increased impact resistance .
  • An additional objective of the present invention is to provide a polymeric composition comprising polymeric particles and colorants for lightning applications giving an aspect contrast and/or color contrast independent of the color of lightning source by using the same polymeric composition, while having a satisfying impact resistance.
  • Another objective of the present invention is to provide a polymeric composition comprising polymeric particles and colorants; so that the composition, when used in a lightning application and the light source is lit on, a lightning device comprising said composition can transmit light over the whole range of wavelength of visible light, while having a satisfying impact resistance.
  • a luminous device comprising a light source and a polymeric composition comprising polymeric particles and colorants that when the light source is lit on, it is hidden and can transmit light over the whole range of wavelength of visible light, having a satisfying impact resistance.
  • the diffusion of light which increases the relative diffusion power and the hiding power is usually increased by adding scattering particles to the composition and the impact strength is increased by adding impact modifiers usually by adding core-shell impact modifiers.
  • the document EP 1864274 discloses an illuminating device combining a LED and a diffusing sheet.
  • the luminous device comprises at least one light-emitting diode and at least one cover made of a transparent plastic in which particles that scatter the light emitted by the light-emitting diode are dispersed.
  • the document EP 1927098 discloses an illuminating device combining a white LED and a diffusing sheet.
  • the luminous device comprises at least one white light-emitting diode and at least one cover made of a transparent plastic in which particles that scatter the light emitted by the light-emitting diode are dispersed
  • the document US 2016/0245954 discloses an optical diffusion blend material for LED lightning.
  • the diffusing blend comprises a mixture of inorganic particles and organic particles.
  • the document W02004/098857 discloses an injection molding method for the production of light diffusing molded items.
  • the molding material comprises a matrix of polymethyl methacrylate and spherical plastic particles with a particle size of 1 to 24pm.
  • a polymeric composition PCI comprising a polymeric phase having a glass transition temperature of at least 50°C, an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CA n , possesses a sufficient hiding power in lightning applications and provides a homogenous light diffusion and impact strenght.
  • a polymeric composition PCI comprising a polymeric phase having a glass transition temperature of at least 50°C, an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CA n , can be used in in lightning applications for providing a sufficient hiding power and homogenous light diffusion and impact strength .
  • the present invention relates to a polymeric composition PCI comprising:
  • the colorant is mixture of colorants CAi to CA n with n>l in the composition PCI .
  • the present invention relates to a process for preparing polymeric composition PCI comprising: a) a polymeric phase having a glass transition temperature of at least 50°C,
  • the colorant is mixture of colorants CAi to CA n with n>l in the composition PCI.
  • the present invention relates to an article comprising polymeric composition PCI comprising:
  • the colorant is mixture of colorants CAi to CA n with n>l in the composition PCI.
  • the present invention relates to the use of a polymeric composition PCI comprising:
  • the colorant is mixture of colorants CAi to CA n with n>l in the composition PCI, for preparation of articles in lightning applications.
  • An additional aspect of the present invention is a lightning device comprising a polymeric composition PCI comprising : a) a polymeric phase having a glass transition temperature of at least 50°C,
  • the colorant is mixture of colorants CAi to CA n with n>l in the composition PCI, in lightning applications .
  • polymeric elastomeric phase is denoted the thermodynamic state of the polymer above its glass transition temperature.
  • alkyl (meth) acrylate is denoted the to both alkyl acrylate and alkyl methacrylate.
  • copolymer as used is denoted that the polymers consists of at least two different monomers.
  • thermoplastic polymer as used, is denoted a polymer that turns to a liquid or becomes more liquid or less viscous when heated and that can take on new shapes by the application of heat and pressure.
  • PMMA methyl methacrylate
  • elastomeric domains having a flexible nature with a glass transition temperature of less than 20°C is denoted a nanostructure by micro phase separation of macromolecular sequences .
  • the phase separation can be a lamellar structure or spheres of nanometer size, that are not cross-linked, contrary to core-shell impact modifiers, where the "soft" rubber core is usually crosslinked.
  • masterbatch as used is understood composition that comprises an additive in high concentration in a carrier material. The additive is dispersed in the carrier material.
  • transparent is denoted a polymeric material that has a total light transmittance of at least 80% according to ASTM D1003-13 for a sheet made out of this material having a thickness of 3 mm.
  • the polymeric composition PCI comprises a) a polymeric phase having a glass transition temperature of at least 50°C, b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, and c) polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and d) colorants CAi to CA n characterized in that the colorant is mixture of colorants CAi to CA n with n>l in the composition PCI. In other words there are at least two different colorants CAi and CA 2 in the polymeric composition PCI.
  • said macromolecular sequences have a glass transition temperature of less than 20°C, preferably of less than 10°C, more preferably of less than 0°C, advantageously of less than -5°C, and more advantageously of less than —10 °C .
  • the elastomeric phase in the composition according to the present invention can be a continuous phase, a semi-continuous phase, or a discontinuous phase.
  • the macromolecular sequence with the flexible nature forming the elastomeric phase is part of a block copolymer with at least one block having a glass transition temperature of less than 20°C, preferably of less than 10°C, more preferably of less than 0°C, advantageously of less than -5°C, and more advantageously of less than -10°C.
  • the block copolymer can be selected from a thermoplastic block copolymer.
  • the thermoplastic block copolymer comprises at least one block which is an acrylic block.
  • the monomers inside this block are alkyl (meth) acrylate monomers, that have been polymerized.
  • the block copolymer is amorphous. More advantageously the block copolymer does not comprise any semicrystalline or crystalline blocks.
  • thermoplastic block copolymer is a thermoplastic acrylic block copolymer.
  • thermoplastic acrylic block copolymer alkyl (meth) acrylate monomers, that have been polymerized .
  • thermoplastic acrylic block copolymer is having a general formula (A) n B in which:
  • n is an integer of greater than or equal to 1,
  • A is: an acrylic or methacrylic homo- or copolymer having a Tg of greater than 50°C, preferably of greater than 80°C, or polystyrene, or an acrylic/ styrene or methacrylic/styrene copolymer; preferably, A is selected from methyl methacrylate (MMA) , phenyl methacrylate, benzyl methacrylate, or isobornyl methacrylate; more preferably, the block A is PMMA or PMMA modified with acrylic or methacrylic comonomers;
  • B is an acrylic or methacrylic homo- or copolymer having a Tg of less than 20°C, preferably comprising monomers selected from methyl acrylate, ethyl acrylate, butyl acrylate (BuA) , ethylhexyl acrylate, styrene (Sty) , or butyl methacrylate, more preferably butyl acrylate (BuA) , said monomers make up at least 50 wt%, preferably 70 wt% of B.
  • the block copolymer is amorphous.
  • the monomer is selected from methyl methacrylate (MMA) , phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, styrene (Sty) , or alpha methylstyrene, or mixtures thereof.
  • the block A is PMMA, or PMMA copolymerized with acrylic or methacrylic comonomers, or polystyrene (PS), or polystyrene (PS) modified with styrenic comonomers.
  • the block B comprises monomers selected from methyl acrylate, ethyl acrylate, butyl acrylate (BuA) , ethylhexyl acrylate or butyl methacrylate and mixtures thereof, more preferably butyl acrylate said monomers make up at least 50 wt%, preferably 70 wt% of block B.
  • the blocks A and/or B can comprise other acrylic or methacrylic comonomers carrying various chemical function groups known to a person skilled in the art, for example acid, amide, amine, hydroxyl, epoxy, or alkoxy, functional groups.
  • the block A can incorporate groups, such as acrylic acid, or methacrylic acid, in order to increase the temperature stability of thereof.
  • Comonomers like styrene can also be incorporated in the block B in order to mismatch the refractive index of the block A.
  • thermoplastic acrylic block copolymer has a structure selected from: ABA, AB, A 3 B and A 4 B.
  • thermoplastic acrylic block copolymer for example can be one of the following triblock copolymers: pMMA-pBuA-pMMA, p (MMAcoMAA) -pBuA-p (MMAcoMAA) , p (MMAcoMAA) -p (BuAcoSty) -p (MMAcoMAA) and p (MMAcoAA) -pBuA-p (MMAcoAA) .
  • the (meth) acrylic block copolymer MBC is p (MMAcoMAA) -p (BuAcoSty) - p (MMAcoMAA)
  • the block copolymer is of MAM type (PMMA-pBuA-PMMA) .
  • the polymers of PMMA type can comprise small amounts of acrylate comonomer in order to improve the temperature stability thereof.
  • small is meant less than 9 wt%, preferably less than 7 wt%, and more preferably less than 6 wt%, of the polymer.
  • the block B represents from 10% to 85%, preferably from 15% to 80%, of the total weight of the block copolymer. [056]
  • the block B has a weight-average molar mass of between 10 000 g/mol and 500 000 g/mol, preferably of between 20 000 g/mol and 300 000 g/mol.
  • the weight average molar mass can be measured by size exclusion chromatography (SEC) .
  • the block copolymers participating in the composition of the matrix can be obtained by controlled radical polymerization (CRP) or by anionic polymerization; the most suitable process according to the type of copolymer to be manufactured will be selected.
  • CRP controlled radical polymerization
  • anionic polymerization the most suitable process according to the type of copolymer to be manufactured will be selected.
  • this will be CRP, in particular in the presence of nitroxides, for the block copolymers of (A) n B type and anionic or nitroxide radical polymerization, for the structures of ABA type, such as the triblock copolymer MAM.
  • Controlled radical polymerization is described in the document for obtaining block copolymers, i.e. international patent application WO 2003/062293.
  • the polymeric phase having a glass transition temperature of at least 50°C can be either the block A of the thermoplastic acrylic block copolymer as describe before or another thermoplastic polymer PI or a mixture of both.
  • thermoplastic polymer PI is selected from polyethylene terephthalate (PET) , polymethyl methacrylate (PMMA) , polycarbonate (PC) , polyvinylidenefluoride (PVDF) , poly (ethylene-vinyl acetate) (PEVA) or polyamide-grafted polyolefin.
  • thermoplastic polymer PI is selected from a homo- or copolymer of methyl methacrylate API .
  • thermoplastic polymer PI can be crosslinked or not.
  • the macromolecular sequence with the flexible nature forming the elastomeric phase is part of a polymer network.
  • the network is crosslinked, preferably in the part of the network that is not the macromolecular sequence with the flexible nature forming the elastomeric phase.
  • the macromolecular sequence with the flexible nature forming the elastomeric phase that is part of a polymer network represents between 1 wt% and 30 wt% of the polymer network comprising the macromolecular sequence with the flexible nature forming the elastomeric phase and the other polymer chains and crosslinkers making up the network.
  • the macromolecular sequence with the flexible nature forming the elastomeric phase, which is part of a polymer network is a thermoplastic acrylic sequence.
  • thermoplastic acrylic sequence By this is meant that at least 50 wt% of the monomers inside thermoplastic acrylic sequence are alkyl (meth) acrylate monomers.
  • the alkyl (meth) acrylate monomers of the macromolecular sequence with the flexible nature forming the elastomeric phase having a Tg of less than 20°C, which is part of a polymer network, comprise monomers selected from methyl acrylate, ethyl acrylate, butyl acrylate (BuA) , 2-ethylhexyl acrylate, styrene or butyl methacrylate, or mixtures thereof.
  • butyl acrylate make up at least 50 wt%, preferably 70 wt% of said monomers of the macromolecular sequence with the flexible nature forming the elastomeric phase having a Tg of less than 20°C, which is part of a polymer network.
  • the polymeric phase having a glass transition temperature of at least 50°C is also part of the network.
  • the polymeric particles PP1 it is having a weight average particle diameter between lpm and lOOpm, preferably a weight average particle diameter between lpm and 90pm, more preferably between lpm and 80pm, advantageously between lpm and 70pm and most advantageously between lpm and 60pm.
  • the polymeric particle PP1 can also be a mixture of different kind of particles. Either it can be particles of the same chemical nature having a different weight average particle diameter, as long as both are within the interval between lpm and lOOprn for weight average particle diameter. Or it can be particles of different chemical nature having the same or a different weight average particle diameter, as long as both are within the interval between lpm and lOOprn for the weight average particle diameter. [071] With regard to the polymeric particles PP1 they can be chosen from silicone particles, (meth) acrylic particles, styrenic particles and mixtures thereof. The particles can be crosslinked or partly crosslinked. The polymeric particles PP1 can be mixtures of different kind of particles.
  • the polymeric particles PP1 has a limited degree of swelling in organic solvents.
  • organic solvent is acetone or (meth) acrylic monomer as methyl methacrylate.
  • degree of swelling refers to the capacity of a particle immersed in a solvent to change in volume.
  • a degree of swelling equal to 0% means that the particle diameter remains unchanged.
  • a degree of swelling of greater than 0% reveals a volume expansion of the particle and a degree of swelling of less than 0% reveals a volume contraction of the particle.
  • a degree of swelling of 100% means that the particle has increased its volume by a factor of 2, which corresponds to an increase in the diameter of the particle of a factor of */2.
  • a degree of swelling of 50% means that the particle has increased its volume by a factor of 1.5, which corresponds to an increase in the diameter of the particle of a factor of TTs .
  • the degree of swelling of the polymeric particles PP1 in aceton or (meth) acrylic monomer shall be less than 100%, preferably less than 50% and advantageously less than 20%.
  • the polymeric silicone particle as polymeric particles PP1, it is having a weight average particle diameter between lpm and 20pm.
  • the silicone particles PP1 comprises polysiloxanes chains having a silicone- oxygen backbone chain.
  • the polymeric silicone particle PP1 has a refractive index between 1.30 and 1.45, preferably between 1.35 and 1.45, advantageously between 1.36 and 1.44.
  • the weight average particle diameter of the polymeric silicone particle PP1 is preferably between Imih and 15pm, more preferably between Imih and 8mm, still more preferably between lpm and 7pm, even more preferably between lpm and 6pm, advantageously between lpm and 5pm and more advantageously between lpm and 4pm.
  • the bulk density of a powder of the polymeric silicone particle PP1 is between O.lg/ml and 0.5g/ml, preferably between 0.15 and 0.47g/ml.
  • the polymeric silicone particle PP1 can for example be prepared according to US 2008/124549.
  • the polymeric silicone particle could also be a blend of two or more different silicone particles PPla, PPlb...., as long as all silicone particles have the before mentioned characteristics.
  • polymeric (meth) acrylic particles as polymeric particles PP1, they are having a weight average particle diameter between lpm and 100pm, it comprises at least 50wt% of monomers coming from acrylic and/or methacrylic monomers in the polymer chains of the polymeric particle PP2.
  • the polymeric (meth) acrylic particle PP1 is a homo- or copolymer of methyl methacrylate (MMA) that comprises at least 50%, preferably at least 60%, advantageously at least 65% and more advantageously at least 70% by weight of methyl methacrylate.
  • MMA methyl methacrylate
  • the weight average particle diameter of the polymeric (meth) acrylic particle PP1 is preferably between lpm and 90pm, more preferably between 2pm and 80pm and advantageously between 2pm and 60pm.
  • the polymeric (meth) acrylic particle PP1 is crosslinked.
  • the weight ratio of the crosslinker in the (meth) acrylic particle PP1 is less than 10wt%.
  • the crosslinker is preferably chosen from an organic compound having at least one acrylic or methacrylic function and a second double bond which can polymerize as well.
  • the polymeric (meth) acrylic particle PP1 has a refractive index between 1.49 and 1.56, preferably between 1.50 and 1.55.
  • the polymeric (meth) acrylic particle PP1 can be prepared according to suspension polymerization.
  • the polymeric (meth) acrylic particle could also be a blend of two or more different (meth) acrylic particles PPla, PPlb...., as long as all particles have the before mentioned characteristics.
  • the colorants CA or CAi to CA n can be a pigment or a dye or a mixture of pigments and dyes.
  • the pigment can be an inorganic pigment or an organic pigment .
  • the colorants CA or CAi to CA n is a mixture of pigments and dyes.
  • the colorants CA or CAi to CA n is a mixture of dyes.
  • the colorants CA or CAi to CA n is a mixture of pigments.
  • the colorants CA is mixture of colorants CAi to CA n with h>1.
  • n is l ⁇ n ⁇ 10 and more preferably l ⁇ n ⁇ 9 More preferably n is a natural number.
  • n is l ⁇ n ⁇ 8.
  • n 1 ⁇ h ⁇ 6.
  • n 2 ⁇ n ⁇ 6.
  • the colorants CAi to CA n are chosen that one colorant CAi is red or yellow or orange or green or blue or violet, and that the other colorant CA 2 is red or yellow or orange or green or blue or violet but has a different colour than the colorant CAi; and that the possible still another colorant CA 3 is red or yellow or orange or green or blue or violet but has a different colour than the colorant CAi and CA 2 ; and so on until colorant Cn .
  • the colorants CAi to CA n are having all a different color.
  • the mixture of colorants CAi to CA n is preferably yielding to grey color.
  • the mixture of colorants CAi to CA n is preferably having following values 20 ⁇ L* ⁇ 80, -20 ⁇ a* ⁇ 20, -20 ⁇ b* ⁇ 20, more preferably 30 ⁇ L* ⁇ 70, -10 ⁇ a* ⁇ 10, -10 ⁇ b* ⁇ 10, still more preferably
  • L denotes the luminosity and extends from 0 (black) to 100 (white) .
  • the value a* measures the red and green of the color: the colors tending toward green have a negative a* value while those tending toward the red have a positive a* value.
  • the b* value measures the blue and the yellow of the color: colors tending toward the yellow have a positive b* value while those tending toward the blue have a negative b* value.
  • the L, a*, b* values are measured using a spectrum colorimeter (especially according to the ASTM E 308 standard) .
  • the mixture of colorants CAi to CA n is chosen that, when blended with a transparent material as for example the polymer PI mentioned earlier, a sheet made of transparent material with colorants absorbs in a homogenous way over the whole spectrum of visible light between 400nm and 700nm.
  • homogenous is meant that the variation of the light transmission is small and varies only in an interval of less than 30% of absolute value. Preferably this variation is less than 25% and advantageously less than 20%.
  • the light transmission is between 5% and
  • Colorants for polymers are known and can be for example chosen from the product lines of the companies Lanxess, Clariant, Synthesia or BASF for pigments and dyes.
  • Solvaperm® dyes and Polysynthren® polymer colorants from Clariant as Yellow 3G, Yellow 2G, Orange 3G, Red 2G, Red G, RED PFS , RED BB, Red Violet R, Violet RSB, Blue 2B, Green, GSB, Green G, Yellow GG, Yellow NG, Red GFP, Violet G, Blue R, Blue RLS, Brown 3RL and Brown R.
  • the colorants are for example derivatives of methane, pyrazolone, quinophtalone, perinone, azo, anthraquinone, coumarine
  • the colorants can be for example:
  • the quantity of the colorants CAi to CA n in the polymeric composition PCI is between 10 weight ppm and 10 000 weight ppm relative to the polymer PI, preferably between 20 weight ppm and 8000 weight ppm, more preferably between 50 weight ppm and 5000 weight ppm.
  • the quantity of the respective colorants is chosen so that mixture of colorants CAi to CA n is preferably has a grey color, as defined before and that the mixture of colorants CAi to CA n when blended with a transparent material as polymer PI, a sheet made out of transparent material with colorants absorbs in a homogenous way over the whole spectrum of visible light between 400nm and 700nm, as also defined before.
  • the quantity of the colorant is chosen on function of its relative colour (tinting) strength. This value can be found in commercial brochures or material data sheets (according to DIN 53235 and expressed in SD1/3 - reduced shade to international standard depth 1/3) .
  • the polymeric composition PCI comprises at least one additional colorant CB, which if different from any of the colorants CAi to CA n already present in the polymeric composition PCI .
  • the colorants CB of the variation of the polymeric composition PCI, it can be a pigment or a dye or a mixture of pigments and dyes.
  • the pigment can be an inorganic pigment or an organic pigment.
  • the colorant CB can be chosen from the same colorants as the colorants CAi to CA n .
  • the elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C makes up at least 1 wt% of the composition, preferably at least 2 wt%, and more preferably at least 5 wt%, based on the three compounds a) , b) c) and d) .
  • composition according to the present invention can optionally also comprise UV absorbers, UV stabilizers, radical inhibitors .
  • the polymeric composition PCI according to the present invention comprising the polymeric phase having a glass transition temperature of at least 50°C, the elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CA n as detailed before, is in form of as sheet, which can be plain or slightly bent or curved.
  • the sheet comprising the polymeric composition PCI of the present invention has a thickness of between 0.5 mm and 500 mm.
  • a first method of preparation of a composition according to the first preferred embodiment of the present invention where the macromolecular sequence with the flexible nature forming the elastomeric phase is part of a block copolymer comprises a blending step of the respective compounds.
  • This first method of preparation of the composition according to the present invention is blending the component comprising the elastomeric phase of macromolecular sequences having a flexible nature with the fluorescent dye, the polymeric phase having a glass transition temperature of at least 50°C is already part of the blockcopolymer .
  • a polymeric composition PCI according to the first preferred embodiment to the invention, it comprises the steps of providing and blending the components a) , b) c) and d) .
  • composition PCI comprises:
  • the colorant is mixture of colorants CAi to CA n with n>l in the composition PCI;
  • said process comprises the step of
  • thermoplastic polymer PI selected from those reported above, could also be blended with.
  • the colorant CB is added.
  • the components could optionally be heated if necessary during blending.
  • Blending could also be obtained by dry blending a solid resin comprising the elastomeric phase of macromolecular sequences having a flexible nature and composition comprising polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CA n.
  • composition according to the first preferred embodiment of the present invention can be transformed by injection molding, extrusion or coextrusion for the preparation of sheets or films.
  • a second method of preparation of a polymeric composition PCI according to the second preferred embodiment of the present invention, where the macromolecular sequence with the flexible nature forming the elastomeric phase is part of a polymer network comprises the steps of mixing the polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CA n with at least one monomer and macromolecular sequences having a flexible nature followed by a polymerisation step .
  • An example for this method for preparation of a composition according to the present invention would be a cast sheet polymerization wherein the polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CA n are mixed with the monomer or monomers and the other ingredients before the polymerization.
  • a method excluding the, is describe in international patent application WO 2012/085487.
  • Said methods for the manufacturing the polymeric composition PCI uses preferably a masterbatch or liquid colour of colorants CAi to CA n .
  • the masterbatch or liquid colour comprises between lOOppm by weight and 50% by weight of colorants.
  • a liquid color is used in a second preferred embodiment for the preparation.
  • An example for liquid color concentrates is given in the document US2009/0156732.
  • said polymeric composition can be advantageously used in lightning devices .
  • the impact performance is obtained due to the elastomeric phase of macromolecular sequences having a flexible nature.
  • the present invention concerns the use of the polymeric composition PCI for making an object.
  • composition PCI according to the invention can be used for making an object or a moulded object or article or be used to be part of an article.
  • object or a moulded object or article or be used to be part of an article made out of the composition according to the invention has a thickness of more than 50pm, more preferably more than lOOprn and even more preferably more than 500pm.
  • Examples for object or articles are covers or plates for luminous devices.
  • the molded object is a cover for a light source.
  • the cover generally has a thickness of between 0.001cm and 15cm, preferably between 0.01cm and 10cm, more preferably between 0.05cm and 7cm, more preferably between 0.1cm and 5cm and even more preferably between 0.2cm and 4cm.
  • the composition obtained from the polymeric composition PCI according to the invention can used as a covering for a point light source.
  • the light source plus cover forms a lightning device.
  • the cover may be a single layer, or may be a multi-layer structure.
  • the cover is separated from the light source by a distance of between 0.1cm and 50 cm, preferably between 1 and 40 cm, preferably between 2 and 20 cm and even more preferably between 3 and 20 cm.
  • a lightning device comprises the polymeric composition PCI according to the invention.
  • the luminous device or lightning device comprises a light source.
  • the light source is a LED.
  • the light source can be a white or a coloured LED.
  • the light source can be a white or a coloured.
  • the light source is preferably a white light source .
  • the lightning device according to the invention has a variety of applications such as, for example:
  • the cover may especially have the form of a letter, a number, a symbol or any other sign
  • the luminous device may be a headlamp, a day running light (DRL) , a fog lamp, a rear lamp, a direction indicator, a stop light, a signature light or an external display.
  • DRL day running light
  • the luminous device may be a headlamp, a day running light (DRL) , a fog lamp, a rear lamp, a direction indicator, a stop light, a signature light or an external display.
  • the weight average molecular weight of polymeric compound can be measure by size exclusion chromatography (SEC) .
  • the glass transition temperature (Tg) of the polymers is measured with differential scanning calorimetry (DSC) according standard ISO 11357-2/2013.
  • optical properties of the polymers are measured according to following method: light transmittance and haze are measured according to the standard ASTM D1003, sheets of 2mm thickness for molded samples. A haze-gard plus apparatus from BYK- Gardner is used. The gloss is measured according to ASTM D523. [Oil] Refractive index is measured with a refractometer .
  • Particle size the particle diameter is measured by Laser diffraction with a Coulter Counter.
  • the three values L, a*, b* are measured by color spectrometry by reflection if the light source is off and by transmission if the light source is lit on.
  • a color spectrometer "Color Sphere" from BYK-Gardner is used.

Abstract

The present invention relates to a polymeric composition comprising a polymeric elastomeric phase, polymeric particles and a colorants. In particular the present invention relates to a polymeric composition comprising a polymeric elastomeric phase polymeric particles and a colorants, its process of preparation and use. The present invention concerns also objects or articles comprising a polymeric composition comprising a polymeric elastomeric phase polymeric particles and a colorants. The present invention concerns as well a lightning or luminous device comprising a polymeric composition comprising a polymeric elastomeric phase polymeric particles and a colorants

Description

Polymeric composition comprising colorants, its process of preparation, use and object comprising it
[Field of the invention]
[001] The present invention relates to a polymeric composition comprising a polymeric elastomeric phase, polymeric particles and a colorants.
[002] In particular the present invention relates to a polymeric composition comprising a polymeric elastomeric phase polymeric particles and a colorants, its process of preparation and use.
[003] The present invention concerns also objects or articles comprising a polymeric composition comprising a polymeric elastomeric phase polymeric particles and a colorants.
[004] The present invention concerns as well a lightning or luminous device comprising a polymeric composition comprising a polymeric elastomeric phase polymeric particles and a colorants.
[Technical problem]
[005] Thermoplastic polymers and especially (meth) acrylic polymers are widely used, including lightning applications. This is mainly due to its characteristics as a highly transparent polymer material with excellent resistance to ultraviolet radiation and weathering. So (meth) acrylic polymers are used for example in lamps, luminaires, light covers, displays, lit shelving, surfaces and illuminated signs.
[006] The lightning applications have various requests on the (meth) acrylic polymers or the compositions based on (meth) acrylic polymers as light transmission, diffusing power. These compositions based on (meth) acrylic polymers comprise generally more or less spherical particles, which are also polymeric particles or other organic particles or inorganic particles.
[007] Additionally it is of also of great interest to have a polymeric composition with a good compromise between light transmission and diffusing properties, hiding the light source and that the light or coloured light is transmitted and diffused when the light source is switched on. Last point is especially important for lightning applications where it is for example required that a sign is to be visible in the daytime when the light source is off or not necessarily switched on; but also at night, or in half-darkness, when the light source is switched on.
[008] This compromise is based on the correct or optimal quantity of the respective particles in the polymeric composition and colorants in the polymeric composition.
[009] Therefore it is important to have a polymeric composition that contains polymeric particles and colorants that can be used in lightning devices that comprises LEDs that can hide the light source and that light or coloured light is transmitted and diffused when the light source is switched on
[010] Furthermore it is of great interest to have long lasting composition or objects that resist highly to impacts and possess an increased flexibility.
[Oil] The objective of the present invention is to provide a polymeric composition comprising polymeric particles and colorants suitable for lightning applications and having an increased impact resistance .
[012] An additional objective of the present invention is to provide a polymeric composition comprising polymeric particles and colorants for lightning applications giving an aspect contrast and/or color contrast independent of the color of lightning source by using the same polymeric composition, while having a satisfying impact resistance.
[013] Another objective of the present invention is to provide a polymeric composition comprising polymeric particles and colorants; so that the composition, when used in a lightning application and the light source is lit on, a lightning device comprising said composition can transmit light over the whole range of wavelength of visible light, while having a satisfying impact resistance.
[014] Again still another objective of the present invention is to provide a luminous device comprising a light source and a polymeric composition comprising polymeric particles and colorants that when the light source is lit on, it is hidden and can transmit light over the whole range of wavelength of visible light, having a satisfying impact resistance.
[BACKGROUND OF THE INVENTION ] Prior art
[015] The diffusion of light which increases the relative diffusion power and the hiding power is usually increased by adding scattering particles to the composition and the impact strength is increased by adding impact modifiers usually by adding core-shell impact modifiers.
[016] The document EP 1864274 discloses an illuminating device combining a LED and a diffusing sheet. The luminous device comprises at least one light-emitting diode and at least one cover made of a transparent plastic in which particles that scatter the light emitted by the light-emitting diode are dispersed.
[017] The document EP 1927098 discloses an illuminating device combining a white LED and a diffusing sheet. The luminous device comprises at least one white light-emitting diode and at least one cover made of a transparent plastic in which particles that scatter the light emitted by the light-emitting diode are dispersed
[018] The document US 2016/0245954 discloses an optical diffusion blend material for LED lightning. The diffusing blend comprises a mixture of inorganic particles and organic particles.
[019] The document W02004/098857 discloses an injection molding method for the production of light diffusing molded items. The molding material comprises a matrix of polymethyl methacrylate and spherical plastic particles with a particle size of 1 to 24pm.
[020] The prior art does not discloses an impact modifed polymeric composition comprising polymeric particles and a mixture of colorants at the same time.
[Brief description of the invention]
[021] Surprisingly, it has been discovered that a polymeric composition PCI comprising a polymeric phase having a glass transition temperature of at least 50°C, an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CAn, possesses a sufficient hiding power in lightning applications and provides a homogenous light diffusion and impact strenght.
[022] It has also been found that a polymeric composition PCI comprising a polymeric phase having a glass transition temperature of at least 50°C, an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CAn, can be used in in lightning applications for providing a sufficient hiding power and homogenous light diffusion and impact strength .
[Detailed description of the invention]
[023] According to a first aspect, the present invention relates to a polymeric composition PCI comprising:
a) a polymeric phase having a glass transition temperature of at least 50°C,
b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C,
c) polymeric particles PP1 having a weight average particle diameter between lpm and lOOpm, and
d) colorants CAi to CAn,
characterized in that the colorant is mixture of colorants CAi to CAn with n>l in the composition PCI .
[024] According to a second aspect, the present invention relates to a process for preparing polymeric composition PCI comprising: a) a polymeric phase having a glass transition temperature of at least 50°C,
b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, c) a polymeric particle PP1 having a weight average particle diameter between lpm and lOOpm, and
d) colorants CAi to CAn,
characterized in that the colorant is mixture of colorants CAi to CAn with n>l in the composition PCI.
[025] According to a third aspect, the present invention relates to an article comprising polymeric composition PCI comprising:
a) a polymeric phase having a glass transition temperature of at least 50°C,
b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C,
c) polymeric particles PP1 having a weight average particle diameter between lpm and lOOpm, and
d) colorants CAi to CAn,
characterized in that the colorant is mixture of colorants CAi to CAn with n>l in the composition PCI.
[026] According to another aspect, the present invention relates to the use of a polymeric composition PCI comprising:
a) a polymeric phase having a glass transition temperature of at least 50°C,
b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C,
c) polymeric particles PP1 having a weight average particle diameter between lpm and lOOpm, and
d) colorants CAi to CAn,
characterized in that the colorant is mixture of colorants CAi to CAn with n>l in the composition PCI, for preparation of articles in lightning applications.
[027] An additional aspect of the present invention is a lightning device comprising a polymeric composition PCI comprising : a) a polymeric phase having a glass transition temperature of at least 50°C,
b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C,
c) polymeric particles PP1 having a weight average particle diameter between lpm and lOOpm, and
d) colorants CAi to CAn,
characterized in that the colorant is mixture of colorants CAi to CAn with n>l in the composition PCI, in lightning applications .
[028] By the term "polymeric elastomeric phase" as used, is denoted the thermodynamic state of the polymer above its glass transition temperature.
[029] By the term "alkyl (meth) acrylate" as used, is denoted the to both alkyl acrylate and alkyl methacrylate.
[030] By the term "copolymer" as used is denoted that the polymers consists of at least two different monomers.
[031] By the term "parts" as used herein, is denoted "parts by weight" .
[032] By the term "thermoplastic polymer" as used, is denoted a polymer that turns to a liquid or becomes more liquid or less viscous when heated and that can take on new shapes by the application of heat and pressure.
[033] By the term "PMMA" as used are denoted homo- and copolymers of methyl methacrylate (MMA) , for the copolymer of MMA the weight ratio of MMA inside the PMMA is at least 50 wt% .
[034] By the term "elastomeric domains having a flexible nature with a glass transition temperature of less than 20°C" is denoted a nanostructure by micro phase separation of macromolecular sequences . The phase separation can be a lamellar structure or spheres of nanometer size, that are not cross-linked, contrary to core-shell impact modifiers, where the "soft" rubber core is usually crosslinked. [035] By the term "masterbatch" as used is understood composition that comprises an additive in high concentration in a carrier material. The additive is dispersed in the carrier material.
[036] By saying that a range from x to y in the present invention, it is meant that the upper and lower limit of this range are included, equivalent to at least x and up to y.
[037] By saying that a range is between x and y in the present invention, it is meant that the upper and lower limit of this range are excluded, equivalent to more than x and less then.
[038] By the term "transparent" as used, is denoted a polymeric material that has a total light transmittance of at least 80% according to ASTM D1003-13 for a sheet made out of this material having a thickness of 3 mm.
[039] The polymeric composition PCI according to the present invention comprises a) a polymeric phase having a glass transition temperature of at least 50°C, b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, and c) polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and d) colorants CAi to CAn characterized in that the colorant is mixture of colorants CAi to CAn with n>l in the composition PCI. In other words there are at least two different colorants CAi and CA2 in the polymeric composition PCI.
[040] With regard to elastomeric phase of macromolecular sequences having a flexible nature, said macromolecular sequences have a glass transition temperature of less than 20°C, preferably of less than 10°C, more preferably of less than 0°C, advantageously of less than -5°C, and more advantageously of less than —10 °C .
[041] The elastomeric phase in the composition according to the present invention can be a continuous phase, a semi-continuous phase, or a discontinuous phase.
[042] In a first preferred embodiment, the macromolecular sequence with the flexible nature forming the elastomeric phase is part of a block copolymer with at least one block having a glass transition temperature of less than 20°C, preferably of less than 10°C, more preferably of less than 0°C, advantageously of less than -5°C, and more advantageously of less than -10°C.
[043] The block copolymer can be selected from a thermoplastic block copolymer. Preferably, the thermoplastic block copolymer comprises at least one block which is an acrylic block. By this, is meant that at least 50 wt% of the monomers inside this block are alkyl (meth) acrylate monomers, that have been polymerized.
[044] Advantageously the block copolymer is amorphous. More advantageously the block copolymer does not comprise any semicrystalline or crystalline blocks.
[045] Most preferably the thermoplastic block copolymer is a thermoplastic acrylic block copolymer. By this is meant that at least 50 wt% of the monomers inside thermoplastic acrylic block copolymer are alkyl (meth) acrylate monomers, that have been polymerized .
[046] The thermoplastic acrylic block copolymer is having a general formula (A) nB in which:
• n is an integer of greater than or equal to 1,
• A is: an acrylic or methacrylic homo- or copolymer having a Tg of greater than 50°C, preferably of greater than 80°C, or polystyrene, or an acrylic/ styrene or methacrylic/styrene copolymer; preferably, A is selected from methyl methacrylate (MMA) , phenyl methacrylate, benzyl methacrylate, or isobornyl methacrylate; more preferably, the block A is PMMA or PMMA modified with acrylic or methacrylic comonomers;
• B is an acrylic or methacrylic homo- or copolymer having a Tg of less than 20°C, preferably comprising monomers selected from methyl acrylate, ethyl acrylate, butyl acrylate (BuA) , ethylhexyl acrylate, styrene (Sty) , or butyl methacrylate, more preferably butyl acrylate (BuA) , said monomers make up at least 50 wt%, preferably 70 wt% of B.
[047] Advantageously, the block copolymer is amorphous. [048] Preferably, in the block A the monomer is selected from methyl methacrylate (MMA) , phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, styrene (Sty) , or alpha methylstyrene, or mixtures thereof. More preferably, the block A is PMMA, or PMMA copolymerized with acrylic or methacrylic comonomers, or polystyrene (PS), or polystyrene (PS) modified with styrenic comonomers.
[049] Preferably the block B comprises monomers selected from methyl acrylate, ethyl acrylate, butyl acrylate (BuA) , ethylhexyl acrylate or butyl methacrylate and mixtures thereof, more preferably butyl acrylate said monomers make up at least 50 wt%, preferably 70 wt% of block B.
[050] Furthermore, the blocks A and/or B, can comprise other acrylic or methacrylic comonomers carrying various chemical function groups known to a person skilled in the art, for example acid, amide, amine, hydroxyl, epoxy, or alkoxy, functional groups. The block A can incorporate groups, such as acrylic acid, or methacrylic acid, in order to increase the temperature stability of thereof.
[051] Comonomers like styrene can also be incorporated in the block B in order to mismatch the refractive index of the block A.
[052] Preferably, said thermoplastic acrylic block copolymer has a structure selected from: ABA, AB, A3B and A4B.
[053] The thermoplastic acrylic block copolymer for example can be one of the following triblock copolymers: pMMA-pBuA-pMMA, p (MMAcoMAA) -pBuA-p (MMAcoMAA) , p (MMAcoMAA) -p (BuAcoSty) -p (MMAcoMAA) and p (MMAcoAA) -pBuA-p (MMAcoAA) . In a first preferred embodiment, the (meth) acrylic block copolymer MBC is p (MMAcoMAA) -p (BuAcoSty) - p (MMAcoMAA) In a second preferred embodiment, the block copolymer is of MAM type (PMMA-pBuA-PMMA) .
[054] It is known to a person skilled in the art that the polymers of PMMA type can comprise small amounts of acrylate comonomer in order to improve the temperature stability thereof. By small is meant less than 9 wt%, preferably less than 7 wt%, and more preferably less than 6 wt%, of the polymer.
[055] The block B represents from 10% to 85%, preferably from 15% to 80%, of the total weight of the block copolymer. [056] The block B has a weight-average molar mass of between 10 000 g/mol and 500 000 g/mol, preferably of between 20 000 g/mol and 300 000 g/mol. The weight average molar mass can be measured by size exclusion chromatography (SEC) .
[057] The block copolymers participating in the composition of the matrix can be obtained by controlled radical polymerization (CRP) or by anionic polymerization; the most suitable process according to the type of copolymer to be manufactured will be selected.
[058] Preferably, this will be CRP, in particular in the presence of nitroxides, for the block copolymers of (A) nB type and anionic or nitroxide radical polymerization, for the structures of ABA type, such as the triblock copolymer MAM. Controlled radical polymerization is described in the document for obtaining block copolymers, i.e. international patent application WO 2003/062293.
[059] In this first preferred embodiment, the polymeric phase having a glass transition temperature of at least 50°C can be either the block A of the thermoplastic acrylic block copolymer as describe before or another thermoplastic polymer PI or a mixture of both.
[060] The thermoplastic polymer PI is selected from polyethylene terephthalate (PET) , polymethyl methacrylate (PMMA) , polycarbonate (PC) , polyvinylidenefluoride (PVDF) , poly (ethylene-vinyl acetate) (PEVA) or polyamide-grafted polyolefin.
[061] Preferably, thermoplastic polymer PI is selected from a homo- or copolymer of methyl methacrylate API .
[062] The thermoplastic polymer PI can be crosslinked or not.
[063] In a second preferred embodiment the macromolecular sequence with the flexible nature forming the elastomeric phase is part of a polymer network. The network is crosslinked, preferably in the part of the network that is not the macromolecular sequence with the flexible nature forming the elastomeric phase.
[064] Preferably, the macromolecular sequence with the flexible nature forming the elastomeric phase that is part of a polymer network represents between 1 wt% and 30 wt% of the polymer network comprising the macromolecular sequence with the flexible nature forming the elastomeric phase and the other polymer chains and crosslinkers making up the network.
[065] Preferably, the macromolecular sequence with the flexible nature forming the elastomeric phase, which is part of a polymer network, is a thermoplastic acrylic sequence. By this is meant that at least 50 wt% of the monomers inside thermoplastic acrylic sequence are alkyl (meth) acrylate monomers.
[066] The alkyl (meth) acrylate monomers of the macromolecular sequence with the flexible nature forming the elastomeric phase having a Tg of less than 20°C, which is part of a polymer network, comprise monomers selected from methyl acrylate, ethyl acrylate, butyl acrylate (BuA) , 2-ethylhexyl acrylate, styrene or butyl methacrylate, or mixtures thereof. More preferably butyl acrylate make up at least 50 wt%, preferably 70 wt% of said monomers of the macromolecular sequence with the flexible nature forming the elastomeric phase having a Tg of less than 20°C, which is part of a polymer network.
[067] In this second preferred embodiment, the polymeric phase having a glass transition temperature of at least 50°C is also part of the network.
[068] If crosslinked, the ratio of the crosslinking is sufficient low, so that the composition according to the present invention can be still thermoformed .
[069] With regard to the polymeric particles PP1, it is having a weight average particle diameter between lpm and lOOpm, preferably a weight average particle diameter between lpm and 90pm, more preferably between lpm and 80pm, advantageously between lpm and 70pm and most advantageously between lpm and 60pm.
[070] The polymeric particle PP1 can also be a mixture of different kind of particles. Either it can be particles of the same chemical nature having a different weight average particle diameter, as long as both are within the interval between lpm and lOOprn for weight average particle diameter. Or it can be particles of different chemical nature having the same or a different weight average particle diameter, as long as both are within the interval between lpm and lOOprn for the weight average particle diameter. [071] With regard to the polymeric particles PP1 they can be chosen from silicone particles, (meth) acrylic particles, styrenic particles and mixtures thereof. The particles can be crosslinked or partly crosslinked. The polymeric particles PP1 can be mixtures of different kind of particles.
[072] In a specific embodiment the polymeric particles PP1 has a limited degree of swelling in organic solvents. One example of an organic solvent is acetone or (meth) acrylic monomer as methyl methacrylate. The term "degree of swelling" as used in the present invention refers to the capacity of a particle immersed in a solvent to change in volume. A degree of swelling equal to 0% means that the particle diameter remains unchanged. A degree of swelling of greater than 0% reveals a volume expansion of the particle and a degree of swelling of less than 0% reveals a volume contraction of the particle. A degree of swelling of 100% means that the particle has increased its volume by a factor of 2, which corresponds to an increase in the diameter of the particle of a factor of */2. A degree of swelling of 50% means that the particle has increased its volume by a factor of 1.5, which corresponds to an increase in the diameter of the particle of a factor of TTs .
[073] In the present invention the degree of swelling of the polymeric particles PP1 in aceton or (meth) acrylic monomer shall be less than 100%, preferably less than 50% and advantageously less than 20%.
[074] With regard to the polymeric silicone particle as polymeric particles PP1, it is having a weight average particle diameter between lpm and 20pm. In a first preferred embodiment the silicone particles PP1 comprises polysiloxanes chains having a silicone- oxygen backbone chain.
[075] The polymeric silicone particle PP1 has a refractive index between 1.30 and 1.45, preferably between 1.35 and 1.45, advantageously between 1.36 and 1.44.
[076] In a first preferred embodiment the weight average particle diameter of the polymeric silicone particle PP1 is preferably between Imih and 15pm, more preferably between Imih and 8mm, still more preferably between lpm and 7pm, even more preferably between lpm and 6pm, advantageously between lpm and 5pm and more advantageously between lpm and 4pm.
[077] The bulk density of a powder of the polymeric silicone particle PP1 is between O.lg/ml and 0.5g/ml, preferably between 0.15 and 0.47g/ml.
[078] The polymeric silicone particle PP1 can for example be prepared according to US 2008/124549.
[079] The polymeric silicone particle could also be a blend of two or more different silicone particles PPla, PPlb...., as long as all silicone particles have the before mentioned characteristics.
[080] With regard to the polymeric (meth) acrylic particles as polymeric particles PP1, they are having a weight average particle diameter between lpm and 100pm, it comprises at least 50wt% of monomers coming from acrylic and/or methacrylic monomers in the polymer chains of the polymeric particle PP2.
[081] In a first preferred embodiment the polymeric (meth) acrylic particle PP1 is a homo- or copolymer of methyl methacrylate (MMA) that comprises at least 50%, preferably at least 60%, advantageously at least 65% and more advantageously at least 70% by weight of methyl methacrylate.
[082] The weight average particle diameter of the polymeric (meth) acrylic particle PP1 is preferably between lpm and 90pm, more preferably between 2pm and 80pm and advantageously between 2pm and 60pm.
[083] Preferably the polymeric (meth) acrylic particle PP1 is crosslinked. The weight ratio of the crosslinker in the (meth) acrylic particle PP1 is less than 10wt%. The crosslinker is preferably chosen from an organic compound having at least one acrylic or methacrylic function and a second double bond which can polymerize as well.
[084] The polymeric (meth) acrylic particle PP1 has a refractive index between 1.49 and 1.56, preferably between 1.50 and 1.55.
[085] The polymeric (meth) acrylic particle PP1 can be prepared according to suspension polymerization. [086] The polymeric (meth) acrylic particle could also be a blend of two or more different (meth) acrylic particles PPla, PPlb...., as long as all particles have the before mentioned characteristics.
[087] With regard to the colorants CA or CAi to CAn, it can be a pigment or a dye or a mixture of pigments and dyes. The pigment can be an inorganic pigment or an organic pigment .
[088] In a first preferred embodiment the colorants CA or CAi to CAn is a mixture of pigments and dyes.
[089] In a second preferred embodiment the colorants CA or CAi to CAn is a mixture of dyes.
[090] In a third preferred embodiment the colorants CA or CAi to CAn is a mixture of pigments.
[091] The colorants CA is mixture of colorants CAi to CAn with h>1. Preferably the value n is l<n<10 and more preferably l<n<9 More preferably n is a natural number.
[092] In a first even more preferred embodiment the value n is l<n<8.
[093] In a second even more preferred embodiment the value n is
2<n<9.
[094] In a third even more preferred embodiment the value n is
2<n<8.
[095] In a fourth even more preferred embodiment the value n is 1<h<6.
[096] In a fifth even more preferred embodiment the value n is 2<n<6.
[097] The colorants CAi to CAn are chosen that one colorant CAi is red or yellow or orange or green or blue or violet, and that the other colorant CA2 is red or yellow or orange or green or blue or violet but has a different colour than the colorant CAi; and that the possible still another colorant CA3 is red or yellow or orange or green or blue or violet but has a different colour than the colorant CAi and CA2; and so on until colorant Cn .
[098] In a first preferred embodiment, the colorants CAi to CAn are having all a different color.
[099] The mixture of colorants CAi to CAn is preferably yielding to grey color. The mixture of colorants CAi to CAn is preferably having following values 20<L*<80, -20<a*<20, -20<b*<20, more preferably 30<L*<70, -10<a*<10, -10<b*<10, still more preferably
30<L*<70, -5<a*<5, -5<b*<5.
[0100] The three values L, a*, b* are used to characterize the principal color in the CIELAB system. L denotes the luminosity and extends from 0 (black) to 100 (white) . The value a* measures the red and green of the color: the colors tending toward green have a negative a* value while those tending toward the red have a positive a* value. The b* value measures the blue and the yellow of the color: colors tending toward the yellow have a positive b* value while those tending toward the blue have a negative b* value. The L, a*, b* values are measured using a spectrum colorimeter (especially according to the ASTM E 308 standard) .
[0101] The mixture of colorants CAi to CAn is chosen that, when blended with a transparent material as for example the polymer PI mentioned earlier, a sheet made of transparent material with colorants absorbs in a homogenous way over the whole spectrum of visible light between 400nm and 700nm. By homogenous is meant that the variation of the light transmission is small and varies only in an interval of less than 30% of absolute value. Preferably this variation is less than 25% and advantageously less than 20%. This is shown in figure 1 for example of (meth) acrylic copolymer API as polymer PI. The highest value is 19%, the lowest value is 9%, which yields to a variation of 10% of the absolute value of light transmission .
[0102] Preferably the light transmission is between 5% and
40%, more preferably between 10% and 30% in a wavelength interval of 400nm-700nm for a sheet of (meth) acrylic polymer API having 2mm thickness comprising colorants CAi to CAn.
[ 0103 ] Colorants for polymers are known and can be for example chosen from the product lines of the companies Lanxess, Clariant, Synthesia or BASF for pigments and dyes. There are the MACROLEX® dyes from Lanxess as Yellow 6G Gran, Yellow 3G Gran, Yellow G Gran, Yellow E2R Gran, Orange 3G Gran, Orange R Gran, Red E2G Gran, Red A, Red EG Gran, Red B, Red 5B Gran, Violet, 3R Gran, Violet B Gran, Blue 3R, Blue RR Gran, Green 5B Gran and Green G. There are the Solvaperm® dyes and Polysynthren® polymer colorants from Clariant as Yellow 3G, Yellow 2G, Orange 3G, Red 2G, Red G, RED PFS , RED BB, Red Violet R, Violet RSB, Blue 2B, Green, GSB, Green G, Yellow GG, Yellow NG, Red GFP, Violet G, Blue R, Blue RLS, Brown 3RL and Brown R.
[0104] The colorants are for example derivatives of methane, pyrazolone, quinophtalone, perinone, azo, anthraquinone, coumarine
[0105] The colorants can be for example:
2.4-dihydro-5-methyl-2-phenyl-4- (phenylazo) -3H-pyrazol-3-one, CAS number[4314-14-l] ;
12H-phthaloperin-12-one, CAS number [6925-69-5]/
8, 9, 10, ll-tetrachloro-12H-phthaloperin-12-one, CAS number [20749- 68-2] ;
3-hydroxy-N- (o-tolyl) -4- [ (2,4, 5-trichlorophenyl ) azo] naphthalene-2- carboxamide, CAS number [6535-46-2];
1.4-diamino-2 , 3-diphenoxyanthraquinone, CAS number [6408-72-6]; l-hydroxy-4- (p-tolylamino) anthracene-9, 10-dione, CAS number [81— 48-3] ;
1.4-Bis (2, 4, 6-trimethylanilino) -9, 10-anthraquinone, CAS number
[116-75-6] ;
1.4-bis (p-tolylamino) anthraquinone [128-80-3] .
[0106] The quantity of the colorants CAi to CAn in the polymeric composition PCI, is between 10 weight ppm and 10 000 weight ppm relative to the polymer PI, preferably between 20 weight ppm and 8000 weight ppm, more preferably between 50 weight ppm and 5000 weight ppm. The quantity of the respective colorants is chosen so that mixture of colorants CAi to CAn is preferably has a grey color, as defined before and that the mixture of colorants CAi to CAn when blended with a transparent material as polymer PI, a sheet made out of transparent material with colorants absorbs in a homogenous way over the whole spectrum of visible light between 400nm and 700nm, as also defined before.
[0107] The quantity of the colorant is chosen on function of its relative colour (tinting) strength. This value can be found in commercial brochures or material data sheets (according to DIN 53235 and expressed in SD1/3 - reduced shade to international standard depth 1/3) . [0108] According to a variation the polymeric composition PCI comprises at least one additional colorant CB, which if different from any of the colorants CAi to CAn already present in the polymeric composition PCI .
[0109] With regard to the colorants CB, of the variation of the polymeric composition PCI, it can be a pigment or a dye or a mixture of pigments and dyes. The pigment can be an inorganic pigment or an organic pigment. The colorant CB can be chosen from the same colorants as the colorants CAi to CAn.
[0110] The elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, makes up at least 1 wt% of the composition, preferably at least 2 wt%, and more preferably at least 5 wt%, based on the three compounds a) , b) c) and d) .
[0111] The composition according to the present invention can optionally also comprise UV absorbers, UV stabilizers, radical inhibitors .
[0112] In a first preferred embodiment, the polymeric composition PCI according to the present invention comprising the polymeric phase having a glass transition temperature of at least 50°C, the elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CAn as detailed before, is in form of as sheet, which can be plain or slightly bent or curved.
[0113] The sheet comprising the polymeric composition PCI of the present invention has a thickness of between 0.5 mm and 500 mm.
[0114] A first method of preparation of a composition according to the first preferred embodiment of the present invention where the macromolecular sequence with the flexible nature forming the elastomeric phase is part of a block copolymer, comprises a blending step of the respective compounds.
[0115] This first method of preparation of the composition according to the present invention is blending the component comprising the elastomeric phase of macromolecular sequences having a flexible nature with the fluorescent dye, the polymeric phase having a glass transition temperature of at least 50°C is already part of the blockcopolymer .
[0116] With regard to the first method for the preparation a polymeric composition PCI according to the first preferred embodiment to the invention, it comprises the steps of providing and blending the components a) , b) c) and d) .
[0117] More particularly process for manufacturing the polymeric composition PCI, said composition PCI comprises:
a) a polymeric phase having a glass transition temperature of at least 50°C,
b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C,c) a polymeric particle PP1 having a weight average particle diameter between lpm and lOOpm,
d) colorants CAi to CAn,
characterized in that the colorant is mixture of colorants CAi to CAn with n>l in the composition PCI;
said process comprises the step of
i) providing:
a) a polymeric phase having a glass transition temperature of at least 50°C,
b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C,
c) polymeric particles PP1 having a weight average particle diameter between lpm and lOOpm, and c) the colorants CAi to CAn
ii) blending the four components a) , b) , c) and d) .
[0118] Optionally another thermoplastic polymer PI, selected from those reported above, could also be blended with.
[0119] Optionally the colorant CB is added.
[0120] The components could optionally be heated if necessary during blending.
[0121] Blending could also be obtained by dry blending a solid resin comprising the elastomeric phase of macromolecular sequences having a flexible nature and composition comprising polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CAn.
[0122] The composition according to the first preferred embodiment of the present invention can be transformed by injection molding, extrusion or coextrusion for the preparation of sheets or films.
[0123] A second method of preparation of a polymeric composition PCI according to the second preferred embodiment of the present invention, where the macromolecular sequence with the flexible nature forming the elastomeric phase is part of a polymer network, comprises the steps of mixing the polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CAn with at least one monomer and macromolecular sequences having a flexible nature followed by a polymerisation step .
[0124] An example for this method for preparation of a composition according to the present invention would be a cast sheet polymerization wherein the polymeric particles PP1 having a weight average particle diameter between lpm and lOOprn and colorants CAi to CAn are mixed with the monomer or monomers and the other ingredients before the polymerization. Such a method, excluding the, is describe in international patent application WO 2012/085487.
[0125] Said methods for the manufacturing the polymeric composition PCI uses preferably a masterbatch or liquid colour of colorants CAi to CAn. The masterbatch or liquid colour comprises between lOOppm by weight and 50% by weight of colorants.
[0126] In a first preferred embodiment of the process for the preparation a polymeric composition PCI a masterbatch is used.
[0127] In a second preferred embodiment for the preparation a polymeric composition PCI a liquid color is used. An example for liquid color concentrates is given in the document US2009/0156732.
[0128] As reported above said polymeric composition can be advantageously used in lightning devices . The impact performance is obtained due to the elastomeric phase of macromolecular sequences having a flexible nature.
[0129] According to a still further aspect the present invention concerns the use of the polymeric composition PCI for making an object.
[0130] The composition PCI according to the invention can be used for making an object or a moulded object or article or be used to be part of an article. Preferably the object or a moulded object or article or be used to be part of an article made out of the composition according to the invention has a thickness of more than 50pm, more preferably more than lOOprn and even more preferably more than 500pm.
[0131] Examples for object or articles are covers or plates for luminous devices.
[0132] In one embodiment the molded object is a cover for a light source. The cover generally has a thickness of between 0.001cm and 15cm, preferably between 0.01cm and 10cm, more preferably between 0.05cm and 7cm, more preferably between 0.1cm and 5cm and even more preferably between 0.2cm and 4cm.
[0133] Additionally according to another aspect of the present invention the composition obtained from the polymeric composition PCI according to the invention can used as a covering for a point light source. The light source plus cover forms a lightning device. The cover may be a single layer, or may be a multi-layer structure. The cover is separated from the light source by a distance of between 0.1cm and 50 cm, preferably between 1 and 40 cm, preferably between 2 and 20 cm and even more preferably between 3 and 20 cm.
[0134] In still another embodiment a lightning device comprises the polymeric composition PCI according to the invention.
[0135] The luminous device or lightning device comprises a light source. Preferably the light source is a LED. The light source can be a white or a coloured LED. [0136] For a lightning device comprising a polymeric composition PCI according to the first preferred embodiment of composition PCI, the light source can be a white or a coloured.
[0137] For a lightning device comprising a polymeric composition PCI according to the second or third preferred embodiment of composition PCI, the light source is preferably a white light source .
[0138] The lightning device according to the invention has a variety of applications such as, for example:
- indoor lighting (ambient Lighting, living room lamps, office lamps , etc . ) ;
- outdoor lighting ( streetlamps, park or garden lamps);
- Lighting or displays for home appliances;
- Lighting or displays for Electric and Electronic goods
- advertising displays;
- illuminated signs (in this case, the cover may especially have the form of a letter, a number, a symbol or any other sign) ;
- industrial lightning;
- interior automotive lighting (signature lighting, ambient
lighting, indication signs, instrument panel, interior displays);
- exterior automotive lightning for example the luminous device may be a headlamp, a day running light (DRL) , a fog lamp, a rear lamp, a direction indicator, a stop light, a signature light or an external display.
Methods of evaluation
[0139] The weight average molecular weight of polymeric compound can be measure by size exclusion chromatography (SEC) .
[0140] The glass transition temperature (Tg) of the polymers is measured with differential scanning calorimetry (DSC) according standard ISO 11357-2/2013.
[010] The optical properties of the polymers are measured according to following method: light transmittance and haze are measured according to the standard ASTM D1003, sheets of 2mm thickness for molded samples. A haze-gard plus apparatus from BYK- Gardner is used. The gloss is measured according to ASTM D523. [Oil] Refractive index is measured with a refractometer .
[012] Particle size: the particle diameter is measured by Laser diffraction with a Coulter Counter.
[0141] The three values L, a*, b* are measured by color spectrometry by reflection if the light source is off and by transmission if the light source is lit on. A color spectrometer "Color Sphere" from BYK-Gardner is used.

Claims

Claims
1. A polymeric composition PCI comprising
a) a polymeric phase having a glass transition temperature of at least 50°C,
b) an elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, and
c) a polymeric particle PP1 having a weight average particle diameter between lpm and lOOpm,
d) colorants CAi to CAn,
characterized in that the colorant is mixture of colorants CAi to CAn with n>l in the composition PCI.
2. The polymeric composition PCI according to claim 1, characterized in that said elastomeric phase of macromolecular sequences with the flexible nature forming the elastomeric phase is part of a block copolymer with at least one block having a glass transition temperature of less than 20°C, preferably of less than 10°C, more preferably of less than 0°C, advantageously of less than -5°C, and more advantageously of less than -10°C.
3. The polymeric composition PCI according to any of claims 1 or 2, characterized in that that said elastomeric phase of macromolecular sequences with the flexible nature is selected from a thermoplastic block copolymer, said thermoplastic block copolymer comprising at least one block which is an acrylic block .
4. The polymeric composition PCI according to claim 3, characterized in that said acrylic block copolymer is having a general formula (A) nB in which:
• n is an integer of greater than or equal to 1,
• A is: an acrylic or methacrylic homo- or copolymer having a Tg of greater than 50°C, preferably of greater than 80°C, or polystyrene, or an acrylic/ styrene or methacrylic/styrene copolymer; preferably, A is selected from methyl methacrylate (MMA) , phenyl methacrylate, benzyl methacrylate, or isobornyl methacrylate; more preferably, the block A is PMMA or PMMA modified with acrylic or methacrylic comonomers;
• B is an acrylic or methacrylic homo- or copolymer having a Tg of less than 20°C, preferably comprising monomers selected from methyl acrylate, ethyl acrylate, butyl acrylate (BuA) , ethylhexyl acrylate, or butyl methacrylate, more preferably butyl acrylate (BuA) , said monomers make up at least 50 wt%, preferably 70 wt% of B .
5. The polymeric composition PCI according to claim 1, characterized in that said elastomeric phase of macromolecular sequences are formed from blocks that are part of a polymer network .
6. The polymeric composition PCI according to claims 5, characterized in that the macromolecular sequence with the flexible nature forming the elastomeric phase that is part of a polymer network represents between 1 wt% and 30 wt% of the polymer network.
7. The polymeric composition PCI according to any of claims 1 to
6, characterized in that the elastomeric phase of macromolecular sequences having a flexible nature with a glass transition temperature of less than 20°C, makes up at least 1 wt% of the composition, preferably at least 2 wt% and more preferably at least 5 wt% based on the three compounds a) , b) and c) .
8. The polymeric composition PCI according to any of claims 1 to
7, characterized in that the macromolecular sequences of said elastomeric phase is having a weight average molecular weight of between 10 000 g/mol and 500 000 g/mol .
9. The polymeric composition PCI according to any of claims 1 to 8, characterized in that the mixture of colorants is having a grey colour.
10. The polymeric composition PCI according to any of claims 1 to
8, characterized in that the mixture of colorants is having following values 20<L*<80, -20<a*<20, -20<b*<20, more preferably 30<L*<70, -10<a*<10, -10<b*<10, still more preferably 30<L*<70, -5<a*<5, -5<b*<5 in the CIELAB system.
11. The polymeric composition PCI according to any of claims 1 to 8, characterized in that the mixture of colorants if blended with a transparent polymer PI or (meth) acrylic polymer API only, yields to a homogenous light transmission in a the wavelength interval of 400nm-700nm.
12. The polymeric composition PCI according to any of claims 1 to 8, characterized in that the quantity of the mixture of colorants in the composition is chosen so that if the mixture of colorants is blended with a transparent polymer PI or (meth) acrylic polymer API only, yields to a light transmission between 10% and 30% in a the wavelength interval of 400nm- 700nm .
13. The polymeric composition PCI according to any of claims 1 to
12, characterized in that the colorants CAi to CAn is a mixture of colorants CAi to CAn and the value n is l<n<10.
14. The polymeric composition PCI according to any of claims 1 to
13, characterized in that the colorants CAi to CAn are derivatives of methane, pyrazolone, quinophtalone, perinone, azo, anthraquinone, coumarine.
15. The polymeric composition PCI according to any of claims 1 to 13, characterized in that the colorants CAi to CAn are chosen from 2, 4-dihydro-5-methyl-2-phenyl-4- (phenylazo) -3H- pyrazol-3-one; 12H-phthaloperin-12-one, CAS number [6925-69- 5];
8, 9, 10, ll-tetrachloro-12H-phthaloperin-12-one; 3-hydroxy-N- (o-tolyl) -4- [ (2, 4, 5- trichlorophenyl ) azo] naphthalene-2-carboxamide;
1.4-diamino-2, 3-diphenoxyanthraquinone;
l-hydroxy-4- (p-tolylamino) anthracene-9, 10-dione;
1.4-Bis (2, 4, 6-trimethylanilino ) -9, 10-anthraquinone; 1, 4- bis (p-tolylamino) anthraquinone
16. The polymeric composition PCI according to any of claims 1 to
15, characterized in that the colorants CAi to CAn are chosen that the light transmission is between 5% and 40%, more preferably between 10% and 30% in a wavelength interval of 400nm-700nm for a sheet of (meth) acrylic polymer API having 2mm thickness and comprising colorants CAi to CAn.
17. The polymeric composition PCI according to claim 16, characterized in that the variation of the light transmission varies in an interval of less than 30% of absolute value.
18. The polymeric composition PCI according to any of claims 1 to
17, characterized in that the colorants CAi to CAn are chosen that one colorant CAi is red or yellow or orange or green or blue or violet, and that the other colorant CA2 is red or yellow or orange or green or blue or violet but has a different colour than the colorant CAi; and that the possible still another colorant CA3 is red or yellow or orange or green or blue or violet but has a different colour than the colorant CAi and CA2; and so on until colorant Cn.
19. The polymeric composition PCI according to any of claims 1 to
18, characterized in that n is between 1 and 9.
20. The polymeric composition PCI according to any of claims 1 to 18, characterized in that n is between 2 and 6.
21. The polymeric composition PCI according to any of claims 1 to 20, characterized in that that quantity of the colorants CAi to CAn in the polymeric composition PCI, is between 10 weight ppm and 10 000 weight ppm.
22. The polymeric composition PCI according to any of claims 1 to 21, characterized in that the colorants is a mixture of pigments and dyes.
23. The polymeric composition PCI according to any of claims 1 to
21, characterized in that the colorants is a mixture of dyes.
24. The polymeric composition PCI according to any of claims 1 to
21, characterized in that the colorants is a mixture of pigments
25. The polymeric composition PCI according to any of claims 1 to
24, characterized in that the polymeric particle PP1 is chosen from silicone particles, (meth) acrylic particles, styrenic particles and mixtures thereof.
26. The polymeric composition PCI according to any of claims 1 to
25, characterized in that the polymeric particle PP1 has a degree of swelling in (meth) acrylic monomer of less than 100%, preferably less than 50% and advantageously less than 20%.
27. The polymeric composition PCI according to any of claims 1 to
26, characterized in that the polymeric particle PP1 is having a weight average particle diameter between lpm and 60pm.
28. The polymeric composition PCI according to any of claims 1 to
27, characterized in that the polymeric composition PCI comprises at least one additional colorant CB, which if different from any of the colorants CAi to CAn already present in the polymeric composition PCI.
29. Method of preparation of the polymeric composition PCI according to any of claims 1 to 28, comprising a blending step of the compounds a) , b) , c) and d) .
30. Method of preparation of a the polymeric composition PCI according to any of claims 1 to 28, comprising the steps of i) mixing the components c) and d) with the monomers or a part of the monomers, that will form a) and/or b) and ii) polymerizing the monomers from step i) .
31. The method according to claim 29 or 30, characterized in that a masterbatch or liquid colour of colorants CAi to CAn is used.
32. A process for manufacturing a lightning device, said process comprises the steps of:
i) providing a polymeric composition PCI according to any of claims 1 to 28
ii) making a cover for the lightning device comprising polymeric composition PCI
iii) combining the cover with a light source.
33. Use of a polymeric composition PCI according to any of claims 1 to 28 in lightning applications or in a lightning device.
34. Use of a polymeric composition PCI according to any of claims 1 to 28 for making an object.
35. Use according to claim 34, characterized in that the object is a cover or plate for a luminous device.
36. Object made of the polymeric composition PCI according to any of claims 1 to 28.
37. A lightning device comprising the polymeric composition PCI according to any of claims 1 to 28.
38. The lightning device according to claim 37, comprising a LED as light source.
39. The lightning device according to claim 38 characterized in that the LED is a white LED.
PCT/EP2019/079167 2018-10-26 2019-10-25 Polymeric composition comprising colorants, its process of preparation, use and object comprising it WO2020084112A1 (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062293A1 (en) 2002-01-22 2003-07-31 Atofina Method of producing and using materials which are reinforced against impact and which contain block copolymers that are obtained by means of controlled radical polymerisation in the presence of nitroxides
WO2004098857A1 (en) 2003-05-06 2004-11-18 Röhm GmbH & Co. KG Method for the production of light-diffusing moulded items with excellent optical characteristics
WO2006100127A2 (en) * 2005-03-25 2006-09-28 Arkema France Illuminating device combining a white led and a diffusing sheet
EP1864274A2 (en) 2005-03-25 2007-12-12 Arkema France Illuminating device combining a led and a diffusing sheet
US20080124549A1 (en) 2006-11-23 2008-05-29 Cheil Industries Inc. Silicone Fine Particles, Method for Preparing the Same, and Thermoplastic Resin Composition Using the Same
US20090156732A1 (en) 2006-04-14 2009-06-18 Polyone Corporation Liquid color concentrate
WO2012085487A1 (en) 2010-12-23 2012-06-28 Arkema France Crosslinked nanostructured cast sheets
US20160245954A1 (en) 2015-02-24 2016-08-25 Arkema France Optical diffusion blend materials for led lighting
WO2018151030A1 (en) * 2017-02-16 2018-08-23 株式会社クラレ Resin composition comprising acrylic block copolymer and light diffusing agent

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062293A1 (en) 2002-01-22 2003-07-31 Atofina Method of producing and using materials which are reinforced against impact and which contain block copolymers that are obtained by means of controlled radical polymerisation in the presence of nitroxides
WO2004098857A1 (en) 2003-05-06 2004-11-18 Röhm GmbH & Co. KG Method for the production of light-diffusing moulded items with excellent optical characteristics
WO2006100127A2 (en) * 2005-03-25 2006-09-28 Arkema France Illuminating device combining a white led and a diffusing sheet
EP1864274A2 (en) 2005-03-25 2007-12-12 Arkema France Illuminating device combining a led and a diffusing sheet
EP1927098A2 (en) 2005-03-25 2008-06-04 ARKEMA France Illuminating device combining a white led and a diffusing sheet
US20090156732A1 (en) 2006-04-14 2009-06-18 Polyone Corporation Liquid color concentrate
US20080124549A1 (en) 2006-11-23 2008-05-29 Cheil Industries Inc. Silicone Fine Particles, Method for Preparing the Same, and Thermoplastic Resin Composition Using the Same
WO2012085487A1 (en) 2010-12-23 2012-06-28 Arkema France Crosslinked nanostructured cast sheets
US20160245954A1 (en) 2015-02-24 2016-08-25 Arkema France Optical diffusion blend materials for led lighting
WO2018151030A1 (en) * 2017-02-16 2018-08-23 株式会社クラレ Resin composition comprising acrylic block copolymer and light diffusing agent

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