COMPOSITION COMPRISING INORGANIC PARTICLES DISPERSED IN A TRANSPARENT MATERIAL

Abstract

In particular the present invention relates to polymeric composition comprising scattering particles for lightning applications or light guides. The invention also relates to a process for manufacturing such a polymeric composition comprising scattering particles for lightning applications or light guides. More particularly the present invention relates to a polymeric (meth)acrylic composition comprising inorganic scattering particles for lightning applications or light guides.

Claims

1. A composition C1 comprising: a) a transparent material M1; and b) inorganic particles P1 comprising an inorganic compound of the formula AB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1 and A, B, and C are cations and X is an anion; or of the formula A′.sub.1-yA″.sub.yCX.sub.3, wherein y is from 0 to 1 and A′, A″, and C are cations and X is an anion; or of the formula A′.sub.1-yA″.sub.yB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1, y is from 0 to 1 and A′, A″, B, and C are cations and X is an anion, the particles P1 having a weight average particle diameter of between 1 nm and 1 μm and representing at least 1000 ppm of the composition C1 comprising the components a) and b).

2. The composition C1 according to claim 1, wherein the composition C1 comprises between 1000 ppm and 10 wt % by weight of the inorganic particles P1 calculated on the components a) and b).

3. The composition C1 according to claim 1, wherein the composition C1 comprises between 1.25 wt % and 10 wt % of the inorganic particles P1 calculated on the components a) and b).

4. The composition C1 according to claim 1, wherein the transparent material M1 is a transparent polymer PO1.

5. The composition C1 according to claim 1, wherein the transparent material M1 is a transparent polymer PO1 composition comprising at least 50 wt % of a (meth)acrylic polymer composition MPCo.

6. The composition C1 according to claim 1, wherein X in all formulas is oxygen O.

7. The composition C1 according to claim 1, wherein A, A′ or A″ in the formulas are chosen from an alkali metal cation or alkali earth metal cation.

8. The composition C1 according to claim 1, wherein A, A′ or A″ in the formulas are chosen from metal cations and A′ is different from A″ and is chosen from cations of calcium, strontium or barium.

9. The composition C1 according to claim 1, wherein the cation C is chosen from a metal cation of an element of UIPAC groups 3 to 7 of the periodic table of elements or from the lanthanides series of chemical elements.

10. The composition C1 according to claim 1, wherein the cation C is chosen from cations of niobium, tantalum, titanium or zirconium.

11. The composition C1 according to claim 1, wherein the cation B is chosen a metal cation of an element of UIPAC groups 3 to 7 of the periodic table of elements or from the lanthanides series of chemical elements and is different from C.

12. The composition C1 according to claim 1, wherein the cation B is chosen from cations of manganese, niobium, tantalum, titanium, zirconium or ytterbium.

13. The composition C1 according to claim 1, wherein the inorganic compound is BaTiO.sub.3or Ba.sub.1-ySr.sub.yTiO.sub.3 or BaZr.sub.xTi.sub.1-xO.sub.3.

14. The composition C1 according to claim 1, wherein weight average particle size of the inorganic particle P1 is between 5 nm and 950 nm

15. The composition C1 according to claim 1, wherein weight average particle size of the inorganic particle P1 is between 30 nm and 900 nm.

16. A process for the preparation of a composition C1 according to claim 1, wherein the process comprises the steps of a) providing inorganic particles P1 b) incorporating the inorganic particles P1 in the transparent material M1.

17. A process for the preparation of a composition C1 according to claim 1, wherein the process comprises the steps of a1) providing inorganic particles P1, a2) providing the transparent material M1, and b) incorporating the inorganic particles P1 in the transparent material M1.

18. The process according to claim 17, wherein the incorporating step is made by blending the inorganic particles P1 with the transparent material M1.

19. A process for the preparation of a composition C2, the process comprising the steps of a) providing a composition C1 according to claim 1; and b) blending the composition C1 with a transparent material M2, wherein the composition C2 comprises less than 1000 ppm of inorganic particles P1.

20. (canceled)

21. (canceled)

22. A process for manufacturing an article for lighting applications comprising: a) providing a composition C1 according to claim 1; and b) transforming the composition C1.

23. An article comprising a composition C1 according to claim 1.

24. The article according to claim 23, wherein the article is in form in form of a sheet, a wedge, a rod or a tube.

25. The article according to claim 23, where the article is a light guide body or a light guide plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0035] According to a first aspect, the present invention relates to a composition C1 comprising [0036] a) a transparent material M1 and, [0037] b) inorganic particles P1 comprising an inorganic compound either of the formula AB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1 and A, B, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yCX.sub.3, wherein y is from 0 to 1 and A′, A″, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1, y is from 0 to 1 and A′, A″, B, and C are cations and X is an anion, said particles are having a weight average particle diameter between 1 nm and 1 μm,
characterized in that the particles P1 represents at least 1000 ppm of the composition C1 comprising the components a) and b).

[0038] According to a second aspect, the present invention relates to the use of a composition C1 comprising [0039] a) a transparent material M1 and, [0040] b) inorganic particles P1 comprising an inorganic compound either of the formula AB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1 and A, B, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yCX.sub.3, wherein y is from 0 to 1 and A′, A″, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1, y is from 0 to 1 and A′, A″, B, and C are cations and X is an anion, said particles are having a weight average particle diameter between 1 nm and 1 μm,
characterized in that the particles P1 at least 1000 ppm of the composition C1 comprising the components a) and b), in lightning applications.

[0041] In a third aspect the present invention relates to a process for the preparation a composition C1 comprising the steps of: [0042] a) providing inorganic particles P1 comprising an inorganic compound either of the formula AB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1 and A, B, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yCX.sub.3, wherein y is from 0 to 1 and A′, A″, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1, y is from 0 to 1 and A′, A″, B, and C are cations and X is an anion, said particles are having a weight average particle diameter between 1 nm and 1 μm, [0043] b) incorporating the particles P1 in a transparent material M1;
characterized in that the particles P1 represents at least 1000 ppm of the composition C1 comprising the components a) and b).

[0044] In a fourth aspect the present invention relates to a process for manufacturing an article for lightning applications comprising the steps of [0045] a) providing a composition C1 as defined before, [0046] b) transforming the composition C1.

[0047] In a fifth aspect the present invention relates to an article comprising a composition C1, said composition C1 comprises [0048] a) a transparent material M1 and, [0049] b) inorganic particles P1 comprising an inorganic compound either of the formula AB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1 and A, B, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yCX.sub.3, wherein y is from 0 to 1 and A′, A″, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1, y is from 0 to 1 and A′, A″, B, and C are cations and X is an anion, said particles are having a weight average particle diameter between 1 nm and 1 μm,
characterized in that the particles P1 represents at least 1000 ppm of the composition C1 comprising the components a) and b).

[0050] According to a sixth aspect, the present invention relates to the use of a composition C1 comprising [0051] a) a transparent material M1 and, [0052] b) inorganic particles P1 comprising an inorganic compound either of the formula AB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1 and A, B, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yCX.sub.3, wherein y is from 0 to 1 and A′, A″, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1, y is from 0 to 1 and A′, A″, B, and C are cations and X is an anion, said particles are having a weight average particle diameter between 1 nm and 1 μm,
characterized in that the particles P1 at least 1000 ppm of the composition C1 comprising the components a) and b), for preparing a composition C2 in that the particles P1 represents less than 1000 ppm.

[0053] In a seventh aspect the present invention relates to a process for the preparation of a composition C2 comprising the steps of: [0054] a) providing a composition C1 comprising [0055] a1) a transparent material M1, and [0056] a2) inorganic particles P1 comprising an inorganic compound either of the formula AB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1 and A, B, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yCX.sub.3, wherein y is from 0 to 1 and A′, A″, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1, y is from 0 to 1 and A′, A″, B, and C are cations and X is an anion, said particles are having a weight average particle diameter between 1 nm and 1 μm, so that the particles P1 represents at least 1000 ppm of the composition C1 comprising the components a1) and a2); [0057] b) blending the composition C1 with a transparent material M2;
characterized in that the particles P1 represents less than 1000 ppm by weight in the composition C2.

[0058] By the term “particle” as used is denoted a more or less spherical polymer comprising particle or inorganic particle in the nanometer range. Preferably the particle has a weight average particle size between 2 nm and 1000 nm.

[0059] By the term “particle size” as used is denoted the weight average diameter of a particle considered as spherical (equivalent sphere having same weight or volume, both connected via density).

[0060] By the term “copolymer” as used is denoted that the polymer consists of at least two different monomers.

[0061] By the term “(meth)acrylic monomer” as used is denoted all kind of acrylic and methacrylic monomers.

[0062] By the term “(meth)acrylic polymer” as used is denoted that the (meth)acrylic) polymer comprises essentially polymers comprising (meth)acrylic monomers that make up 50 wt % or more of the (meth)acrylic polymer.

[0063] By the term “transparent” as used is denoted that the respective material has a light transmittance according to ASTM D-1003 (sheet of 3 mm thickness) of at least 85%.

[0064] 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.

[0065] 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 than y.

[0066] According to the invention, preferred embodiments for different respective characteristics of the respective components can be combined in any combination. As for example the preferred transparent polymer PO1 as transparent material M1 with preferred weight average particle diameter di of the inorganic particle P1; or as for example the preferred embodiment of the (meth)acrylic polymer MP1 with preferred choices of cations A, A′ or A″ of inorganic compound of inorganic particle P1.

[0067] With regard to the composition C1 of the invention, it comprises a) transparent material M1 and b) inorganic particles P1 comprising a an inorganic compound either of the formula AB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1 and A, B, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yCX.sub.3, wherein y is from 0 to 1 and A′, A″, and C are cations and X is an anion; or inorganic particle P1 comprises an inorganic compound the formula A′.sub.1-yA″.sub.yB.sub.xC.sub.1-xX.sub.3, wherein x is from 0 to 1, y is from 0 to 1 and A′, A″, B, and C are cations and X is an anion; said particles are having a weight average particle diameter between 1 nm and 1 μm.

[0068] Preferably the numbers x and y in the formulas are a rational number from 0 to 1.

[0069] The relative weight quantity of the inorganic particles P1 is at least 1000 ppm by weight of the composition C1 comprising the components a) and b).

[0070] Preferably the quantity of the inorganic particles P1 is between 1000 ppm and 10 wt %.

[0071] In a first more preferred embodiment the composition C1 comprises between 1000 ppm and 10 000 ppm by weight of the inorganic particles P1 in the composition C1 calculated on the components a) and b).

[0072] In a second more preferred embodiment the composition C1 comprises between 1 wt % and 10 wt % by weight of the inorganic particles P1 in the composition C1 calculated on the components a) and b).

[0073] In a third more preferred embodiment the composition C1 comprises between 1000 ppm and 5000 ppm by weight of the inorganic particles P1 in the composition C1 calculated on the components a) and b).

[0074] In a fourth more preferred embodiment the composition C1 comprises between 5000 ppm and 10 wt % by weight of the inorganic particles P1 in the composition C1 calculated on the components a) and b).

[0075] In a fifth more preferred embodiment the composition C1 comprises between 1.25 wt % and 10 wt % by weight of the inorganic particles P1 in the composition C1 calculated on the components a) and b)

[0076] The composition C1 can comprise also other compounds, which are not taken into account for the calculation of the weight ratios between the two compounds a) and b).

[0077] The composition C1 can comprise for example impact modifiers, colorants.

[0078] With regard to the transparent material M1, it is chosen from glass or transparent polymers.

[0079] In a first preferred embodiment, the transparent material M1 is a transparent polymer PO1. The polymer PO1 can be thermoplastic polymer or thermoset polymer. In case of the thermoplastic polymer it is also considered as part of the invention that the thermoplastic polymer can be crosslinked or slightly crosslinked as long as a piece of this polymer can still be formed and change shape, as for example by thermoforming.

[0080] The transparent polymer PO1 can be chosen from (meth) acrylic polymers, polycarbonate, polystyrenes, polyesters, polyvinylchloride (PCV), cyclic olefin copolymers, styrene methyl methacrylate (SMMA), styrene acrylonitrile (SAN), polyvinylidene fluoride (PVDF) and blends thereof.

[0081] In a first preferred embodiment the transparent polymer PO1 is a composition comprising at least 50 wt % of a (meth)acrylic polymer composition MPCo, preferably at least 60 wt % and more preferably at least 70 wt %.

[0082] In a second preferred embodiment the transparent polymer PO1 is a (meth)acrylic polymer composition MPCo.

[0083] The (meth)acrylic polymer composition MPCo can be chosen from a (meth)acrylic block copolymer or a (meth)acrylic polymer MP1 or a crosslinked (meth) acrylic composition MCX.

[0084] With regard to the (meth)acrylic polymer MP1 it is a polymeric polymer chain comprising at least 50 wt % of monomers coming acrylic and/or methacrylic monomers. The (meth)acrylic polymer MP1 could also be a mixture of two or more (meth)acrylic polymer AP1 to APx.

[0085] The acrylic and/or methacrylic monomers are chosen from acrylic acid, methacrylic acid, esters of acrylic acid of esters of methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof.

[0086] Preferably the monomer is chosen from acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group having from 1 to 22 carbons, either linear, branched or cyclic; preferably the alkyl group having from 1 to 12 carbons, either linear, branched or cyclic.

[0087] Advantageously the (meth)acrylic monomer is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-butyl acrylate, iso-butyl acrylate, n-butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and mixtures thereof.

[0088] Other comonomers can be copolymerized with the acrylic and/or methacrylic monomers as long as the (meth)acrylic polymer AP1 is comprising at least 50 wt % of monomers coming acrylic and/or methacrylic monomers in its polymeric chain. The other comonomers can be chosen from styrenic monomers as styrene or styrene deriviatives, acrylonitrile, vinylesters as vinylacetate. The amount of these comonomers is from 0 wt % to 50 wt %, preferably from 0 wt % to 40 wt %, more preferably from 0 wt % to 30 wt %, advantageously from 0 wt % to 20 wt %.

[0089] In a first more preferred embodiment the (meth)acrylic polymer MP1 is a thermoplastic homo- or copolymer of methyl methacrylate (MMA) that comprises at least 50%, preferably at least 60%, advantageously at least 70% and more advantageously at least 80% by weight of methyl methacrylate.

[0090] The copolymer of methyl methacrylate (MMA) comprises between 50% and 99.9% by weight of methyl methacrylate and between 0.1 and 50% by weight of at least one monomer having at least one ethylenic unsaturation that can copolymerize with methyl methacrylate.

[0091] These monomers are well known and mention may be made, in particular of acrylic and methacrylic acids and alkyl(meth)acrylates in which the alkyl group has from 1 to 12 carbon atoms. As examples, mention may be made of methyl acrylate and ethyl, butyl or 2-ethylhexyl (meth)acrylate. Preferably the comonomer is an alkyl acrylate in which the alkyl group having from 1 to 4 carbon atoms.

[0092] According to the first more preferred embodiment the copolymer of methyl methacrylate (MMA) comprises from 60% to 99.9% advantageously from 70% to 99.9% and more advantageously from 80% to 99.9% by weight of methyl methacrylate and from 0.1% to 40% advantageously from 0.1% to 30% and more advantageously from 0.1% to 20% by weight of at least one monomer having at least one ethylenic unsaturation that can copolymerize with methyl methacrylate. Preferably the comonomer is chosen from methyl acrylate or ethyl acrylate or mixtures thereof.

[0093] The (meth)acrylic polymer MP1can optionally have a melt flow index (MFI) according to ISO 1133 (230° C./3.8 kg) between 0.1 g/10 min and 20 g/10 min. Preferably melt flow index can be between 0.2 g/10 min and 18 g/10 min, more preferably between 0.3 g/10 min and 16 g/10 min, advantageously between 0.4 g/10 min and 13 g/10 min.

[0094] The (meth)acrylic polymer MP1 has a refractive index between 1.46- and 1.52, preferably between 1.47 and 1.52 and more preferably between 1.48 and 1.52.

[0095] The (meth)acrylic polymer MP1 has a light transmittance according to ASTM D-1003 (sheet of 3 mm thickness) of at least 85%, preferably 86%, more preferably 87%.

[0096] The (meth)acrylic polymer MP1 has a Vicat softening temperature of at least 90° C. The Vicat softening temperature is measured according to ISO 306:2013 (B50 method).

[0097] The composition according to the invention can comprise beside the (meth)acrylic polymer MP1 also an (meth)acrylic polymer MP2. The (meth)acrylic polymer MP1 and (meth)acrylic polymer MP2 form a mixture or a blend. This mixture or blend consists of at least one homopolymer and at least one copolymer of MMA, or a mixture of at least two homopolymers or two copolymers of MMA with a different average molecular weight or a mixture of at least two copolymers of MMA with a different monomer composition.

[0098] In a second more preferred embodiment the (meth)acrylic polymer MP1 is crosslinked homo- or copolymer of methyl methacrylate (MMA) that comprises at least 50%, preferably at least 60%, advantageously at least 70% and more advantageously at least 80% by weight of methyl methacrylate.

[0099] The (meth)acrylic polymer MP1 of the second preferred embodiment comprises as well as crosslinker. Preferably the crosslinker is a copolymerzable compound having at least two double bonds.

[0100] In a third more preferred embodiment the (meth)acrylic polymer composition MPCo is a (meth)acrylic block copolymer MBC of methyl methacrylate (MMA) that comprises at least 50% of methyl methacrylate.

[0101] The (meth)acrylic block copolymer MBC comprises at least one block having a glass transition temperature less than 20° C. preferably less than 10° C. more preferably less than 0° C., advantageously less than −5° C. and more advantageously less than −10° C.

[0102] Preferably (meth)acrylic block copolymer MBC comprises at least one block which is an (meth)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.

[0103] Most preferably the (meth)acrylic block copolymer MBC comprises least 50 wt % of the monomers inside (meth)acrylic block copolymer MBC are alkyl(meth)acrylate monomers, that have been polymerized.

[0104] The (meth)acrylic block copolymer MBC is having a general formula (A).sub.nB in which: [0105] n is an integer of greater than or equal to 1, [0106] 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 chosen from methyl methacrylate (MMA), phenyl methacrylate, benzyl methacrylate or isobornyl methacrylate. Preferably, the block A is PMMA or PMMA modified with acrylic or methacrylic comonomers; [0107] B is an acrylic or methacrylic homo- or copolymer having a Tg of less than 20° C., preferably comprising monomers chosen of methyl acrylate, ethyl acrylate, butyl acrylate (BuA), ethylhexyl acrylate, styrene (Sty) or butyl methacrylate, more preferably butyl acrylate said monomers make up at least 50 wt %, preferably 70 wt % of B.

[0108] Advantageously the (meth)acrylic block copolymer MBC is amorphous.

[0109] Preferably, in the block A the monomer is chosen 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 PS modified with styrenic comonomers.

[0110] Preferably the block B comprises monomers chosen of 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.

[0111] 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 (MAA), in order to increase the temperature stability of thereof.

[0112] Comonomers like styrene can also be incorporated in the block B in order to mismatch the refractive index of the block A.

[0113] Preferably, said thermoplastic acrylic block copolymer has a structure chosen from: ABA, AB, A.sub.3B and A.sub.4B.

[0114] The (meth)acrylic block copolymer MBC 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).

[0115] 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.

[0116] The block B represents from 10% to 85%, preferably 15% to 80% of the total weight of the block copolymer MBC.

[0117] The block B has a weight-average molar mass of between 10 000 g/mol and 500 000 g/mol, preferably from 20 000 g/mol to 300 000 g/mol. The weight average molar mass can be measured by size exclusion chromatography (SEC).

[0118] The (meth)acrylic block copolymers 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 chosen.

[0119] Preferably, this will be CRP, in particular in the presence of nitroxides, for the (meth)acrylic block copolymers of (A).sub.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. in WO03/062293.

[0120] The (meth)acrylic block copolymer MBC can be transformed by extrusion or injection molding in form of a object.

[0121] In a fourth more preferred embodiment the (meth)acrylic polymer composition MPCo is a crosslinked (meth) acrylic composition MCX. consisting of a brittle matrix (I) having a glass transition temperature Tg of greater than 0° C. and of elastomeric domains having a characteristic dimension of less than 100 nm consisting of macromolecular sequences (II) having a flexible nature with a glass transition temperature of less than 0° C., characterized that the macromolecular sequences (II) having a flexible nature are having a weight average molecular weight Mw of between 150 000 g/mol and 800 000 g/mol.

[0122] As regards the matrix (I), it exhibits an overall Tg of greater than 0° C., measured by differential scanning calorimetry (DSC), and is compatible with the methyl methacrylate homo- or copolymer. Preferably glass transition temperature Tg is greater than 10° C., more preferably greater than 20° C., still more preferably greater than 40° C. even more preferably greater than 45° C., advantageously greater than 50° C. and more advantageously greater than 60° C.

[0123] The matrix (I) is prepared from methyl methacrylate and optionally one or more monomer(s) Mol chosen from: [0124] acrylic monomers of formula CH.sub.2═CH—C(═O)—O—R.sub.1, where R.sub.1 denotes a hydrogen atom or a linear, cyclic or branched C.sub.1-C.sub.40 alkyl group optionally substituted by a halogen atom or a hydroxyl, alkoxy, cyano, amino or epoxy group, such as, for example, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyalkyl acrylates or acrylonitrile; [0125] methacrylic monomers of formula CH.sub.2═C(CH.sub.3)—C(═O)—O—R.sub.2, where R.sub.2 denotes a hydrogen atom or a linear, cyclic or branched C.sub.1-C.sub.40 alkyl group optionally substituted by a halogen atom or a hydroxyl, alkoxy, cyano, amino or epoxy group, such as, for example, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, hydroxyalkyl methacrylates or methacrylonitrile; [0126] vinylaromatic monomers, such as, for example, styrene or substituted styrenes, such as α-methylstyrene, monochlorostyrene or tert-butylstyrene.

[0127] The comonomer(s) are chosen in nature and quantity that the lower limit of the glass transition temperature Tg is met.

[0128] Preferably methyl methacrylate is the predominant monomer in the polymer of the matrix (I). The matrix (I) thus includes a proportion of methyl methacrylate of from 51 wt % to 100 wt %, preferably between 75 wt % and 100 wt % and advantageously between 90 wt % and 100 wt %.

[0129] As regards the macromolecular sequences (II) having a flexible nature, said macromolecular sequences (II) they are also called block B in the present invention. These macromolecular sequences (II) having a flexible nature exhibit a glass transition temperature of less than 0° C. (denoted Tg and measured by DSC). Preferably the Tg is less than −5° C., more preferably less than −10° C. and even more preferably less than −15° C.

[0130] Furthermore, the weight-average molecular weight of the macromolecular sequences (II) having a flexible nature with a glass transition temperature of less than 0° C. is between 150 000 g/mol and 800 000 g/mol.

[0131] Preferably the weight-average molecular weight of the macromolecular sequences (II) having a flexible nature with a glass transition temperature of less than 0° C. is between 175 000 and 700 000 g/mol, more preferably between 200 000 g/mol and 650 000 g/mol, and advantageously between 225 000 g/mol and 600 000 g/mol.

[0132] The polydispersity index of the molecular weight Mw/Mn of the macromolecular sequences (II) having a flexible nature or block B is greater than 2, preferably greater than 2.5 and more preferably greater than 3.

[0133] The polydispersity index of the molecular weight Mw/Mn is between 2.5 and 10.0, preferably between 3.0 and 10.0, more preferably between 3.0 and 6.0 and even more preferably between 3.0 and 5.0.

[0134] With regard to the inorganic particle P1 according to the invention, it has a weight average particle size between 1 nm and 1 μm.

[0135] Preferably the weight average particle size of the inorganic particle P1 is more than 5 nm, more preferably more than 10 nm, still more preferably more than 20 nm, again still more preferably more than 30 nm, advantageously more than 40 nm, even more advantageously more than 50 nm and advantageously more than 100 nm.

[0136] Preferably the weight average particle size of the inorganic particle P1 is less than 950 nm, more preferably less than 925 nm, still more preferably less than 900 nm, again still more preferably less than 875 nm, advantageously less than 850 nm, even more advantageously less than 800 nm and advantageously less than 750 nm.

[0137] Preferably the weight average particle size of the inorganic particle P1 is between 5 nm and 950 nm, more preferably between 10 nm and 950 nm, still more preferably between 20 nm and 900 nm, again still more preferably between 30 nm and 900 nm, advantageously between 40 nm and 850 nm, even more advantageously between 50 nm and 800 nm and advantageously between 100 nm and 750 nm.

[0138] The inorganic particle P1 comprises either an inorganic compound of the formula (1a)

AB.sub.xC.sub.1-xX.sub.3   (1a)

[0139] wherein x is from 0 to 1 and A, B, and C are cations and X is an anion;

[0140] or inorganic particle P1 comprises an inorganic compound the formula (1b)

A′.sub.1-yA″.sub.yCX.sub.3   (1b)

[0141] wherein y is from 0 to 1 and A′, A″, and C are cations and X is an anion;

[0142] or inorganic particle P1 comprises an inorganic compound the formula (1c)

A′.sub.1-yA″.sub.yB.sub.xC.sub.1-xX.sub.3   (1c)

[0143] wherein x is from 0 to 1, y is from 0 to 1 and A′, A″, B, and C are cations and X is an anion

[0144] In one embodiment in formula (1a) and (1c) x is 0 or 1. In another embodiment in formula (1b) and (1c) y is 1 or 0. If x=0 and y=0, the formulas (1a), (1b) and (1c) are simplified to formula ACX3.

[0145] The inorganic compound of the formulas (1a), (1b) and (1c) represents from 50 wt % to 100 wt % of the inorganic particle P1. Preferably the inorganic compound of the formulas (1a), (1b) and (1c) represents from 60 wt % to 100 wt % of the inorganic particle P1, more preferably from 70 wt % to 100 wt %, still more preferably from 75 wt % to 100 wt %, advantageously from 80 wt % to 100 wt % and advantageously from 90 wt % to 100 wt %.

[0146] In a first preferred embodiment the X in all formulas (1a), (1b) and (1c) is oxygen O.

[0147] The cations A, A′ or A″ the formulas (1a), (1b) and (1c) are chosen from metal cations and A′ is different from A″. Preferably A, A′ or A″ is an alkali metal cation or alkali earth metal cation, more preferably chosen from cations of lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, lanthanum or lead. Still more preferably A, A′ or A″ is chosen from cations of lithium, sodium, potassium, beryllium, magnesium, calcium, strontium or barium. Advantageously A, A′ or A″ is chosen from cations of magnesium, calcium, strontium or barium and still more advantageously A, A′ or A″ is chosen from cations of calcium, strontium or barium

[0148] The cation C is chosen from a metal cation of an element of UIPAC groups 3 to 7 of the periodic table of elements or from the lanthanides series of chemical elements. Preferably the cation C is chosen from cations of manganese, niobium, tantalum, titanium, zirconium or ytterbium. More preferably the cation C is chosen from cations of niobium, tantalum, titanium or zirconium.

[0149] The cation B is chosen from a metal cation of an element of UIPAC groups 3 to 7 of the periodic table of elements or from the lanthanides series of chemical elements and is different from C. Preferably B is chosen from cations of manganese, niobium, tantalum, titanium, zirconium or ytterbium. More preferably the cation B is chosen from cations of niobium, tantalum, titanium or zirconium.

[0150] Examples of compounds of formulas (1a), (1b) and (1c) are LiTaO.sub.3, LiNbO.sub.3, KNbO.sub.3, BaTiO.sub.3, KTaO.sub.3, PbZrO.sub.3, PbZr.sub.xTi.sub.1-xO.sub.3, Ba.sub.ySr.sub.1-yTiO.sub.3, SrTiO.sub.3, LaMnO.sub.3, LaMnO.sub.3, La.sub.yCa.sub.1-yTiO.sub.3, LaYbO.sub.3 and CaTiO.sub.3.

[0151] More preferably, the compound of the formulas (1a), (1b) and (1c) has perovskit structure.

[0152] More preferably the cation A, A′ or A″ in formula (1) has an ionic radii of at least 100 μm. Advantageously the cation A, A′ or A″ in formula (1) has an ionic radii of at least 105 μm and more advantageously at least 110 μm.

[0153] More preferably the cations B and C in formula (1) have an ionic radii of less than 100 μm. Advantageously the cations B and C in formula (1) have an ionic radii of less than 95 μm and more advantageously less than 90 μm.

[0154] The ionic radii of the respective ions can be found in encyclopaedias. In a particular first preferred embodiment the inorganic compound of formula (1a) is BaTiO.sub.3.

[0155] In a particular second preferred embodiment the compound of formula (1b) is Ba.sub.1-ySr.sub.yTiO.sub.3, with 0<y<1.

[0156] In a particular third preferred embodiment the compound of formula (1a) is BaZr.sub.xTi.sub.1-xO.sub.3 with 0<x<1.

[0157] With regard to the process for the preparation of the composition C1 according to the invention it comprises the steps of [0158] a) providing inorganic particles P1 [0159] b) incorporating the inorganic particles P1 in the transparent material M1.

[0160] Advantageously the process for for manufacturing the composition C1 according to the invention it comprises the steps of [0161] a1) providing inorganic particles P1, [0162] a2) providing the transparent material M1, [0163] b) incorporating the inorganic particles P1 in the transparent material M1.

[0164] The respective inorganic particles P1 and the transparent material M1 and their respective embodiments are the same as defined before.

[0165] The incorporating step can be made either by blending the inorganic particles P1 with the transparent material M1, or the incorporation step is divided into two sub steps, where the inorganic particles P1 are blended with a precursor of the transparent material M1 comprising monomers followed by polymerization.

[0166] With regard to the process for the preparation of the composition C2 from the composition C1 according to the invention it comprises the steps of comprises the steps of [0167] a) providing a composition C1, [0168] b) blending the composition C1 with a transparent material M2;
so that the composition C2 comprises less than 1000 ppm by weight of inorganic particles P1.

[0169] In this process for the preparation of the composition C2, the composition C1 serves as a masterbatch. This is also the aspect of the use of the composition C1 to prepare a composition C2 comprising less than 1000 ppm of inorganic particles P1.

[0170] The transparent material M2 in blending step b) is in excess of the composition C1.

[0171] In a first embodiment weight ratio of the transparent material M2 to composition C1 in blending step b) is above 2, preferably above 5, more preferably above 10.

[0172] In a second embodiment weight ratio of the transparent material M2 to composition C1 in blending step b) is above 5, preferably above 20, more preferably above 50.

[0173] In a third embodiment weight ratio of the transparent material M2 to composition C1 in blending step b) is above 10, preferably above 50, more preferably above 100.

[0174] In a fourth embodiment weight ratio of the transparent material M2 to composition C1 in blending step b) is between 2 and 10.sup.6.

[0175] Preferably the composition C2 comprises between 0.1 ppm and 1000 ppm by weight of the inorganic particles P1.

[0176] In a first more preferred embodiment the composition C2 comprises between 0.1 ppm and 100 ppm by weight of the inorganic particles P1 in the composition C1 calculated on the components a) and b).

[0177] In a second more preferred embodiment the composition C2 comprises between 10 ppm and 1000 ppm by weight of the inorganic particles P1 in the composition C1 calculated on the components a) and b).

[0178] In a third more preferred embodiment the composition C2 comprises between 100 ppm and 1000 ppm by weight of the inorganic particles P1 in the composition C1 calculated on the components a) and b).

[0179] In a fourth more preferred embodiment the composition C2 comprises between 1 ppm and 5 ppm by weight of the inorganic particles P1 in the composition C1 calculated on the components a) and b).

[0180] With regard to the transparent material M2, it is chosen from glass or transparent polymers.

[0181] Preferably the transparent material M2 is chosen from the same materials as the transparent material M1.

[0182] In the composition C2 the transparent material M2 and the transparent material M1 can be the same.

[0183] In a first preferred embodiment the transparent material M2 is also a transparent polymer P1. The polymer P1 is the same as defined before.

[0184] The composition C1 according to the invention can be used directly in lightning applications or in an article suitable for lightning applications.

[0185] According to an additional aspect the present invention concerns a process for manufacturing an article for lightning applications comprising the steps of [0186] a) providing a composition C1 or a composition C2, [0187] b) transforming the composition C1 or C2.

[0188] The article can be a cover for a light source or a light emitting device or light guide body or light guide plate, depending on the quantity of the particles in the composition.

[0189] The light emitting device can be a light-emitting diode (LED) or laser diode (LD)

[0190] The composition C1 or C2 can for example be used in lightning applications or in an article suitable for lightning applications in form of a sheet, a wedge, a rod or a tube.

[0191] The sheet is having a thickness between 0.5 mm and 300 mm, preferably between 1 mm and 200 mm.

[0192] The wedge is having on its largest thickness between 4 mm and 300 mm, preferably between 5 mm and 200 mm.

[0193] The rod or the tube is having a diameter between 0.5 mm and 300 mm.

[0194] The sheets or rods or tubes or wedges manufactured from or with the composition C2 can be used as light guide body or light guide plate, for example as edge lightning.

[0195] The light guide body or plate according to the invention preferably has at least a thickness of 0.5 mm. The light guide body or plate according to the invention preferably has at most a thickness of 50 mm. The thickness particularly preferably lies in the range of from 1 mm to 30 mm and more particularly preferably is from 2 mm to 25 mm.

[0196] The light guide body or plate may, also be assigned further layers, for example mirror or reflection layers.

Methods of Evaluation

Transmission and Haze

[0197] The luminous transmittance (transmission) and haze is measured on the respective sheets according to the standard ASTM D1003.

Molecular Weight

[0198] The mass average molecular weight (Mw) of the polymers is measured with by size exclusion chromatography (SEC). The chromatography column is calibrated with PMMA standards having a molecular weight between 402 g/mol and 1 900 000 g/mol. The average molecular weight are expressed in g/mol for the number and average molecular weight Mn and Mw respectively. For the measurement, the concentration of the polymer is 1 g/L.

Particle Size Analysis

[0199] The particle size of the scattering particles is measured with scanning electron microscopy (SEM). At least 50 particles are counted. The diameter of the particle size is the one of the circle filling the same area as the 2D image projection of the particle. The weight average particle size is calculated.

Refractive Index

[0200] The refractive index n is measured or taken at 589 nm at 20° C. with a refractometer.

EXAMPLES

[0201] As transparent material M1 a PMMA copolymer of methyl methacrylate as injection molding grade is used, having a melt flow index of 8 g/10 min.

[0202] As comparative particles TiO.sub.2 is used. The used TiO.sub.2 particles have a weight average particle diameter of about 500 nm.

[0203] As exemplified particles of type P1, BaTiO.sub.3 is used. The used BaTiO.sub.3 particles have a weight average particle diameter of about 500 nm.

[0204] The respective particles were provided and incorporated in the PMMA matrix at a loading of 1.5 wt % by blending the two components, yielding to a composition of type C1. The composition is white.

[0205] The composition of type C1 is blended in a further step with transparent material M2, which is the same PMMA copolymer of methyl methacrylate having a melt flow index of 8 g/10 min. The quantity of M2 is chosen that a two different composition of type C2 are obtained comprising respectively 20 ppm by weight and 100 ppm by weight of the respective particles.

[0206] Followed is the preparation of a sheet of 3 mmm thickness by injection molding of the PMMA composition type C2 with 20 ppm by weight and 100 ppm by weight of the respective particles.

[0207] The luminous transmittance (transmission) and haze is measured on the respective sheets according to the standard ASTM D1003. A haze-gard plus apparatus from BYK-Gardner is used.

TABLE-US-00001 TABLE 1 results Transmission Haze Example (visible) [%] [%] Comparative sheet with TiO.sub.2 83 15.6 Example sheet with BaTiO.sub.3 89 6.08

[0208] As shown in table 1 the transmission of the composition type C2 is higher, while the haze is lower.

[0209] The transmission is also measured as function of the wavelength λ in the visible light for both concentrations of particle loadings.

TABLE-US-00002 TABLE 2 transmission at 20 ppm particles as function of wavelength λ Transmission [%] Wavelength λ Comparative sheet Example sheet [nm] with TiO.sub.2 with BaTiO.sub.3 380 80 87 400 81 88 450 81 89 500 82 89 550 82 89 600 83 89 650 83 89 700 84 89 750 85 89 800 85 89

TABLE-US-00003 TABLE 3 transmission at 100 ppm particles as function of wavelength λ Transmission [%] Wavelength λ Comparative sheet Example sheet [nm] with TiO.sub.2 with BaTiO.sub.3 380 50 80 400 55 80 450 57 80 500 57 80 550 58 80 600 59 80 650 61 80 700 62 80 750 64 80 800 65 80

[0210] Table 2 and 3 show a higher light transmission that is much less independent of the wavelength for the composition C2 made from a composition C1 according to the invention.