EP3870647A1 - Composition polymérique comprenant un colorant, son procédé de préparation, son utilisation et objet le comprenant - Google Patents

Composition polymérique comprenant un colorant, son procédé de préparation, son utilisation et objet le comprenant

Info

Publication number
EP3870647A1
EP3870647A1 EP19795171.8A EP19795171A EP3870647A1 EP 3870647 A1 EP3870647 A1 EP 3870647A1 EP 19795171 A EP19795171 A EP 19795171A EP 3870647 A1 EP3870647 A1 EP 3870647A1
Authority
EP
European Patent Office
Prior art keywords
polymeric composition
colorants
composition pci
polymeric
cai
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19795171.8A
Other languages
German (de)
English (en)
Inventor
Jean-Marc Boutillier
Benoît ANDRE
Sylvain QUERUEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Trinseo Europe GmbH
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP3870647A1 publication Critical patent/EP3870647A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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

La présente invention concerne une composition polymérique comprenant une phase élastomérique polymérique et un colorant. En particulier, la présente invention concerne une composition polymérique comprenant des particules polymériques en phase élastomérique polymérique et un colorant, son processus de préparation et d'utilisation. La présente invention concerne également des objets ou des articles comprenant une composition polymérique comprenant une phase élastomérique polymérique et un colorant. La présente invention concerne également un dispositif éclairant ou lumineux comprenant une composition polymérique comprenant des particules polymériques en phase élastomérique et un colorant.
EP19795171.8A 2018-10-26 2019-10-25 Composition polymérique comprenant un colorant, son procédé de préparation, son utilisation et objet le comprenant Withdrawn EP3870647A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1859974A FR3087777B1 (fr) 2018-10-26 2018-10-26 Composition de polymere comprenant des colorants, son procede de preparation, son utilisation et objet comprenant celle-ci
PCT/EP2019/079167 WO2020084112A1 (fr) 2018-10-26 2019-10-25 Composition polymérique comprenant un colorant, son procédé de préparation, son utilisation et objet le comprenant

Publications (1)

Publication Number Publication Date
EP3870647A1 true EP3870647A1 (fr) 2021-09-01

Family

ID=65763558

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19795171.8A Withdrawn EP3870647A1 (fr) 2018-10-26 2019-10-25 Composition polymérique comprenant un colorant, son procédé de préparation, son utilisation et objet le comprenant

Country Status (3)

Country Link
EP (1) EP3870647A1 (fr)
FR (1) FR3087777B1 (fr)
WO (1) WO2020084112A1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100551524B1 (ko) 2002-01-22 2006-02-13 아르끄마 니트록사이드 존재하에 조절된 라디칼 중합에 의해 수득된 블락 코폴리머를 함유하며 충격 강화된 물질의 제조 및 사용 방법
DE10320318A1 (de) 2003-05-06 2004-12-02 Röhm GmbH & Co. KG Verfahren zur Herstellung von lichtstreuenden Formteilen mit hervorragenden optischen Eigenschaften
WO2006100126A2 (fr) 2005-03-25 2006-09-28 Arkema France Dispositif d'eclairage combinant une del et une feuille de diffusion
WO2006100127A2 (fr) * 2005-03-25 2006-09-28 Arkema France Dispositif illumine a del blanche et feuille de diffusion
EP2010604B1 (fr) 2006-04-14 2015-02-18 PolyOne Corporation Concentre de couleur liquide
KR100756676B1 (ko) 2006-11-23 2007-09-07 제일모직주식회사 실리콘계 미립자, 그 제조 방법, 및 그 미립자가 함유된열가소성 수지 조성물
FR2969633B1 (fr) 2010-12-23 2015-02-06 Arkema France Composition pour des plaques coulees nanostructurees reticulees
US9557445B2 (en) 2015-02-24 2017-01-31 Arkema France Optical diffusion blend materials for LED lighting
CA3052233A1 (fr) * 2017-02-16 2018-08-23 Kuraray Co., Ltd. Composition de resine comprenant un copolymere a blocs acryliques et un agent de diffusion de la lumiere

Also Published As

Publication number Publication date
FR3087777B1 (fr) 2021-10-01
WO2020084112A1 (fr) 2020-04-30
FR3087777A1 (fr) 2020-05-01

Similar Documents

Publication Publication Date Title
US20210371640A1 (en) A polymer composition comprising particles and colorant, its method of preparation and its use
US9422426B2 (en) Transparent thermoplastic resin composition and molded article using the same
CA2558179A1 (fr) Feuille resistant au vieillissement climatique permettant de colorer en jaune un moulage retroreflechissant
TWI583733B (zh) 光擴散聚合物組成物、其製造方法，及由其製得之物件
CN102971384B (zh) 含热稳定分散添加剂的用于聚（甲基）丙烯酸酯着色的水基液体色料
US11319433B2 (en) Light scattering polymeric composition with improved scattering efficiency and improved mechanical properties
US10907039B2 (en) (Meth)acrylic composition comprising particles, its method of preparation, its use and object comprising it
EP3870647A1 (fr) Composition polymérique comprenant un colorant, son procédé de préparation, son utilisation et objet le comprenant
CN1754911B (zh) 光漫射聚碳酸酯树脂组合物
CN109791217B (zh) 包含颗粒的(甲基)丙烯酸系组合物、其制备方法及其作为母料的用途
US20210380796A1 (en) A polymer composition suitable for injection moulding comprising particles and colorant, its method of preparation and its use
KR20170084652A (ko) 자외선을 흡수하는 반응형 형광 염료 및 이를 포함하는 형광 아크릴 시트
KR20200115551A (ko) 입자를 포함하는 (메트)아크릴릭 중합체 조성물, 이의 제조 방법 및 마스터배치로서의 이의 용도

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210526

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TRINSEO EUROPE GMBH

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20230503