EP1629044A1 - Corps faconnes pour la publicite lumineuse et leur procede de production - Google Patents

Corps faconnes pour la publicite lumineuse et leur procede de production

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Publication number
EP1629044A1
EP1629044A1 EP04716221A EP04716221A EP1629044A1 EP 1629044 A1 EP1629044 A1 EP 1629044A1 EP 04716221 A EP04716221 A EP 04716221A EP 04716221 A EP04716221 A EP 04716221A EP 1629044 A1 EP1629044 A1 EP 1629044A1
Authority
EP
European Patent Office
Prior art keywords
shaped body
scattering particles
weight
meth
plastic
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Withdrawn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
EP04716221A
Other languages
German (de)
English (en)
Inventor
Hans Lichtenstein
Günther Ittmann
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.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
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 Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1629044A1 publication Critical patent/EP1629044A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene

Definitions

  • Shaped body for illuminated advertising and process for its production
  • the present invention relates to moldings for illuminated advertising and methods for producing these moldings.
  • Neon signs are used in many ways. In many cases plastics are used as moldings, which contain scattering agents, so that the illuminants cannot be recognized per se.
  • the publication JP 11-172019 describes mixtures of tech polymer SBX 4, Tospearl 2000 and inorganic scattering media, but the size of the inorganic particles is limited to up to 1 ⁇ m or greater than 8 ⁇ m.
  • the moldings are produced by extrusion, the gloss of the surface not being shown.
  • the publication JP 2-194058 discloses light-scattering plastic bodies for light advertising, the body being composed of a PMMA matrix and scattering particles. Silicone particles with a size in the range of 1 to 6 ⁇ m can be mixed with BaSO 4 particles with a size of 1 to 7 ⁇ m.
  • the proportion of plastic particles is larger than the inorganic particles, which are described as an optional component.
  • the minimum proportion of plastic particles in the shaped bodies is only described as a basis weight, so that this size depends on the thickness of the bodies, which is not set out, however. In the examples, the proportion of plastic particles is at least 0.75% by weight.
  • the moldings are produced by extrusion, the gloss of the surface not being shown.
  • the shaped bodies described above already have a good property profile.
  • Another object of the invention was that the moldings have a high durability, in particular a high resistance to UV radiation or weathering.
  • the moldings should have the highest possible mechanical stability. Furthermore, the invention was based on the object of providing moldings which can be produced particularly easily. For example, the moldings should be able to be produced in particular by casting processes which are carried out fully automatically.
  • Another object of the present invention was to provide moldings which can be easily adapted in size and shape to the requirements.
  • the present invention was based on the object of providing moldings for neon signs which have a low yellowness index. This yellowness index should remain low even when heated to temperatures necessary for forming.
  • claim 20 provides a solution to the underlying problem.
  • moldings comprising a poly (meth) acrylate matrix, 0.05 to 0.5 wt .-% plastic scattering particles having a size in the range of 5 to 15 microns and 0.1 to 3 wt .-% inorganic Scattering particles with a size in the range of 1 to 7.5 microns, it is possible to provide moldings for illuminated advertising that can be reshaped both at high temperatures without the surface becoming matt and also being very resistant.
  • the following advantages in particular are achieved by the measures according to the invention:
  • the moldings of the present invention can be adapted to individual needs without the appearance of the surface being impaired thereby.
  • the moldings of the present invention can be produced in a particularly simple manner.
  • the moldings can thus be produced in particular by casting processes, which are carried out fully automatically.
  • the moldings according to the invention show a high resistance to weathering, in particular to UV radiation.
  • the moldings according to the invention have a particularly low yellowness index, which remains relatively low even after prolonged heating.
  • the size and shape of the moldings can be adapted to the needs.
  • the molded body of the present invention has from 0.05 to 0.5% by weight, preferably 0.05 to 0.4% by weight and particularly preferably 0.1 to 0.3% by weight, of scattering particles comprising plastic on the weight of the molded body.
  • the size of these plastic particles is in the range from 5 to 15 ⁇ m, preferably 6 to 12 ⁇ m and particularly preferably 7 to 11 ⁇ m.
  • the scattering particles comprising plastic which can be used according to the invention are known per se, the type of plastic from which the scattering particles are produced being largely uncritical.
  • the refraction of the light takes place at the phase boundary of the scattering particles comprising the plastic and the matrix plastic.
  • the refractive index of the plastic particles has a refractive index n 0 measured at the Na-D line (589 nm) and at 20 ° C., which is 0.003 to 0.2, in particular 0.02 to 0.2, units of the refractive index n 0 of the matrix plastic differs.
  • the scattering particles comprising plastic preferably contain crosslinked polystyrene, polysilicon and / or crosslinked poly (meth) acrylates, these particles preferably being spherical.
  • plastic particles that are used as scattering agents contain silicones. Such particles are obtained, for example, by hydrolysis and polycondensation of organotrialkoxysilanes and / or tetraalkoxysilanes, which have the formulas
  • R 1 represents, for example, a substituted or unsubstituted alkyl group, an alkenyl group or a phenyl group
  • R 2 of the hydrolyzable alkoxy group represents an alkyl group such as methyl, ethyl or butyl or an alkoxy-substituted hydrocarbon group such as 2-methoxyethyl or 2 Represents ethoxyethyl.
  • Exemplary organotrialkoxysilanes are methyltrimethoxysilane, methyltriethoxysilane, methyl-n-propoxysilane, methyltriisopropoxysilane and methyltris (2-methoxyethoxy) silane.
  • silane compounds and processes for producing spherical silicone particles therefrom are known to those skilled in the art and can be found in the documents EP 1 116 741, JP 63-077940 and JP 2000-186148.
  • Spreading agents made of silicone that are particularly preferably used in the present invention are available from GE Bayer Silicones under the trade names TOSPEARL® 120 and TOSPEARL® 3120.
  • Scatter particles comprising preferred plastic are composed of: b1) 25 to 99.9 parts by weight of monomers which have aromatic groups as substituents, such as, for example, styrene, ⁇ -methylstyrene, ring-substituted styrenes, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 3-phenylpropyl (meth) acrylate or vinyl benzoate; and b2) 0 to 60 parts by weight of an acrylic and / or methacrylic acid ester with 1 to 12 carbon atoms in the aliphatic ester radical, which can be copolymerized with the monomers b1), examples of which are: methyl (meth) acrylate, ethyl ( meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (me
  • Trimethylolpropane tri (meth) acrylate where the comonomers b1), b2) and b3) add up to 100 parts by weight.
  • the plastic comprising scattering particles particularly preferably have at least 80% by weight of styrene and at least 0.5% by weight of divinylbenzene.
  • the production of networked, plastic-comprising scattering particles is known in the specialist world.
  • the scattering particles can be produced by emulsion polymerization, as described, for example, in EP-A 342 283 or EP-A 269 324, very particularly preferably by polymerization in the organic phase, as described, for example, in German patent application P 43 27 464.1, with the latter Polymerization technology, particularly narrow particle size distributions or, to put it another way, particularly small deviations of the particle diameter from the mean particle diameter occur.
  • Scattering particles comprising plastic are particularly preferably used, which have a temperature resistance of at least 200 ° C., in particular of at least 250 ° C., without any intention that this should impose a restriction.
  • temperature-resistant means that the particles are essentially not subject to thermal degradation. Thermal degradation undesirably leads to discoloration, making the plastic material unusable.
  • Particularly preferred particles are available from Sekisui, among others, under the trade names ⁇ Techpolymer SBX-6, ⁇ Techpolymer SBX-8 and ® Techpolymer SBX-12.
  • the shaped body of the present invention has 0.1 to 3% by weight, preferably 0.2 to 2.5% by weight and particularly preferably 0.3 to 2% by weight, of inorganic scattering particles, based on the weight of the shaped body ,
  • the size of these inorganic scattering particles is in the range from 1 to 7.5 ⁇ m, preferably 2 to 5 ⁇ m and particularly preferably 3 to 4 ⁇ m, preferred inorganic scattering particles being spherical.
  • the inorganic scattering particles likewise have a refractive index for the Na-D line (589 nm) and a refractive index n 0 measured at 20 ° C., which is 0.003 to 0.2, in particular 0.02 to 0.2, units of the refractive index n 0 of the matrix plastic differs.
  • Inorganic scattering particles are also known per se and can be obtained commercially. These particles include, in particular, aluminum hydroxide, aluminum-potassium silicate (mica), aluminum silicate (kaolin), barium sulfate (BaSO 4 ), calcium carbonate, magnesium silicate (talc).
  • the proportion of inorganic scattering particles in the shaped body is greater than or equal to the proportion of scattering particles comprising plastic.
  • the weight ratio of the scattering particles comprising plastic to the inorganic scattering particles is preferably in the range from 1: 1 to 1:20, in particular 1: 1, 5 to 1:15 and particularly preferably 1: 2 to 1:10.
  • the particle size and the particle size distribution can be determined using a laser extinction method.
  • a Galay-CIS from LOT GmbH can be used for this, the measuring method for determining the particle size and the particle size distribution being contained in the user manual.
  • the person skilled in the art is aware of the size distribution of particles, the particle sizes described above relating to the weight average. Scattering particles with a narrow size distribution are preferably used. According to a particular aspect of the present invention, the light-scattering particles are spherical.
  • spherical denotes that the particles preferably have a spherical shape, it being obvious to the person skilled in the art that, due to the production methods, particles with a different shape may also be present, or that the shape of the particles may deviate from the ideal spherical shape.
  • the term spherical means that the ratio of the largest dimension of the particles to the smallest dimension is a maximum of 4, preferably a maximum of 2, these dimensions being measured in each case by the center of gravity of the particles. At least 70, particularly preferably at least 90%, based on the number of particles, is preferably spherical.
  • these scattering particles are present in the plastic matrix in a uniformly distributed manner, without any significant aggregation or aggregation of the particles occurring. Evenly distributed means that the concentration of particles within the plastic matrix is essentially constant.
  • the shaped body comprises a plastic matrix which has polymethyl methacrylate (PMMA).
  • PMMA polymethyl methacrylate
  • the shaped body preferably comprises at least 30% by weight, in particular at least 70% by weight and particularly preferably at least 90% by weight, based on the weight of the shaped body, of polymethyl methacrylate.
  • Polymethyl methacrylates are generally obtained by radical polymerization of mixtures containing methyl methacrylate.
  • these mixtures contain at least 40% by weight, preferably at least 60% by weight and particularly preferably at least 80% by weight, based on the weight of the monomers, of methyl methacrylate.
  • these mixtures for the production of polymethyl methacrylates can contain further (meth) acrylates which can be copolymerized with methyl methacrylate.
  • the term (meth) acrylates encompasses methacrylates and acrylates and mixtures of the two.
  • (Meth) acrylates derived from saturated alcohols such as, for example, methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate and
  • Aryl (meth) acrylates such as benzyl (meth) acrylate or
  • Phenyl (meth) acrylate where the aryl radicals can in each case be unsubstituted or substituted up to four times;
  • Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate,
  • Glycol di (meth) acrylates such as 1,4-butanediol (meth) acrylate,
  • Trimethyloylpropantri (meth) acrylate Trimethyloylpropantri (meth) acrylate.
  • compositions to be polymerized can also have further unsaturated monomers which are copolymerizable with methyl methacrylate and the aforementioned (meth) acrylates.
  • 1-alkenes such as 1-hexene, 1-heptene
  • branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methylpentene-1;
  • Styrene substituted styrenes with an alkyl substituent in the side chain, such as. B. ⁇ -methyl styrene and ⁇ -ethyl styrene, substituted styrenes with an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes;
  • Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylipyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiophene, vinylthiolthene hydrogenated vinyl thiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles; Vinyl and isoprenyl ether;
  • Maleic acid derivatives such as maleic anhydride, methyl maleic anhydride, maleimide, methyl maleimide; and dienes such as divinylbenzene.
  • these comonomers are used in an amount of 0 to 60% by weight, preferably 0 to 40% by weight and particularly preferably 0 to 20% by weight, based on the weight of the monomers, the compounds being used individually or can be used as a mixture.
  • the polymerization is generally started with known radical initiators.
  • the preferred initiators include the azo initiators well known in the art, such as AIBN and 1-azobiscyclohexane carbonitrile, and also peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert.-butyl per-2-ethylhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, and tert-Butylperoxybenzoate, tert-Butylperoxyisopropyl carbonate, 2,5-bis (2-ethylhexanoyl-peroxy) -2,5-dimethylhexane, tert-Butylperoxy-2-ethylhexanoate, tert-Butylperoxy-3,5,5-trimethylhexanoate, dicumyl peroxide , 1, 1-bis (tert
  • the weight average molecular weight M w of the homopolymers and / or copolymers to be used according to the invention as matrix polymers can vary within wide ranges, the molecular weight usually being matched to the intended use and the processing mode of the matrix. In general, however, it is in the range between 20,000 and 10,000,000 g / mol, preferably 50,000 to 3,000,000 g / mol and particularly preferably 80,000 to 1,500,000 g / mol, without any intention that this should impose a restriction.
  • the matrix of the shaped body has at least 70, preferably at least 80 and particularly preferably at least 90% by weight, based on the weight of the shaped body, of polymethyl methacrylate.
  • the poly (meth) acrylics of the matrix of the moldings have a refractive index measured at the Na-D line (589 nm) and at 20 ° C. in the range from 1.46 to 1.54.
  • the molding compositions for the production of the moldings can contain customary additives of all kinds. These include, among other things, antistatic agents, antioxidants, mold release agents, flame retardants, lubricants, dyes, flow improvers, fillers, light stabilizers, UV absorbers and organic phosphorus compounds such as phosphites or phosphonates, pigments, weathering protection agents and plasticizers.
  • additives include, among other things, antistatic agents, antioxidants, mold release agents, flame retardants, lubricants, dyes, flow improvers, fillers, light stabilizers, UV absorbers and organic phosphorus compounds such as phosphites or phosphonates, pigments, weathering protection agents and plasticizers.
  • the amount of additives is limited to the application.
  • the light-scattering properties of the moldings and their transparency should not be adversely affected by additives.
  • the molding composition can optionally be given a mechanically more stable finish by means of an impact modifier.
  • the impact modifier for polymethacrylate plastics is well known, so the manufacture and construction of impact modified polymethacrylate molding compositions are described, inter alia, in EP-A 0 113 924, EP-A 0 522 351, EP-A 0 465 049 and EP-A 0 683 028.
  • Preferred impact-resistant molding compositions which can be used to produce the matrix have 70-99% by weight of polymethyl methacrylates. These polymethyl methacrylates have been previously described.
  • the polymethyl methacrylates used for the preparation of impact-modified molding compositions are obtained by radical polymerization of mixtures which contain 80 to 100% by weight, preferably 90 to 98% by weight, methyl methacrylate and optionally 0 to 20% by weight. %, preferably 2-10% by weight of further free-radically polymerizable comonomers, which were also listed above.
  • Particularly preferred comonomers include C 1 -C 4 -alkyl (meth) acrylates, in particular methyl acrylate, ethyl acrylate or butyl methacrylate.
  • the average molecular weight M w of the polymethyl methacrylates which can be used to produce the impact-modified matrix is preferably in the range from 90,000 g / mol to 200,000 g / mol, in particular 100,000 g / mol to 150,000 g / mol.
  • Preferred impact-resistant molding compositions which can be used to produce the matrix contain 1 to 30, preferably 2 to 20, particularly preferably 3 to 15, in particular 5 to 12% by weight of one Impact modifier, which is an elastomer phase made of crosslinked polymer particles.
  • the impact modifier can be obtained in a manner known per se by bead polymerization or by emulsion polymerization.
  • Preferred impact modifiers are crosslinked particles with an average particle size in the range from 50 to 1000 nm, preferably 60 to 500 nm and particularly preferably 80 to 120 nm.
  • Such particles can be obtained, for example, by the radical polymerization of mixtures which generally have at least 40% by weight, preferably 50 to 70% by weight, methyl methacrylate, 20 to 80% by weight, preferably 25 to 35% by weight.
  • the preferred comonomers include, among others, dC 4 -alkyl (meth) acrylates, such as ethyl acrylate or butyl methacrylate, preferably methyl acrylate, or other vinyl-polymerizable monomers, such as, for. B. styrene.
  • the mixtures for producing the abovementioned particles can preferably comprise 0 to 10, preferably 0.5 to 5% by weight of comonomers.
  • Particularly preferred impact modifiers are polymer particles which have a two, particularly preferably a three-layer core-shell structure.
  • core-shell polymers are described, inter alia, in EP-A 0 113 924, EP-A 0 522 351, EP-A 0 465 049 and EP-A 0 683 028.
  • Particularly preferred impact modifiers based on acrylate rubber have the following structure, among others:
  • Core polymer with a methyl methacrylate content of at least 90% by weight, based on the weight of the core.
  • Shell 1 polymer with a butyl acrylate content of at least 80% by weight, based on the weight of the first shell.
  • Shell 2 polymer with a methyl methacrylate content of at least 90% by weight, based on the weight of the second shell.
  • the core and the shells can each contain other monomers in addition to the monomers mentioned. These were set out above, with particularly preferred comonomers having a crosslinking effect.
  • a preferred acrylate rubber modifier can have the following structure:
  • the ratio of core to shell (s) of the acrylate rubber modifiers can vary within wide ranges.
  • the weight ratio core to shell KS is in the range from 20:80 to 80:20, preferably from 30:70 to 70:30 to modifiers with a shell or that Ratio of core to shell 1 to shell 2 K / S1 / S2 in the range from 10:80:10 to 40:20:40, particularly preferably from 20:60:20 to 30:40:30 for modifiers with two shells.
  • the particle size of the core-shell modifiers is usually in the range from 50 to 1000 nm, preferably 100 to 500 nm and particularly preferably from 150 to 450 nm, without any intention that this should impose a restriction.
  • Such impact modifiers are commercially available from Mitsubishi under the trade name METABLEN® IR 441.
  • impact-modified molding compounds can also be obtained.
  • Particularly preferred molding compositions for the production of the plastic matrix are commercially available from Röhm GmbH & Co. KG.
  • the molded body can be produced by known processes, thermoplastic molding processes being preferred. After the particles have been added, shaped articles can be produced from the molding compositions described above by conventional thermoplastic molding processes.
  • the shaped bodies can be produced by casting processes.
  • suitable (meth) acrylic mixtures are given in a mold and polymerized.
  • Such (meth) acrylic mixtures generally have the (meth) acrylates set out above, in particular methyl methacrylate.
  • the (meth) acrylic mixtures can contain the copolymers set out above and, in particular for adjusting the viscosity, polymers, in particular poly (meth) acrylates.
  • the present invention surprisingly enables the viscosity to be set to a predetermined value. As a result, the casting process for the production of moldings for illuminated advertising can be automated.
  • a suitable acrylic resin includes, for example
  • the acrylic resin has the initiators necessary for the polymerization.
  • Components A to D and the initiators correspond to the compounds which are also used to produce suitable polymethyl methacrylate molding compositions.
  • the acrylic resins may include known additives that have been exemplified above. In addition, additives can be used to prevent the scattering particles from settling.
  • the weight average molecular weight M w of the polymers produced by casting chamber processes is generally higher than the molecular weight of polymers used in molding compositions. This results in a number of known advantages. In general, the weight average molecular weight of polymers which are produced by casting chamber processes is in the range from 500,000 to 10,000,000 g / mol, without any intention that this should impose any restriction.
  • the thickness of the shaped body is generally in the range from 0.05 to 200 mm, preferably in the range from 0.1 to 30 mm, without any intention that this should impose a restriction.
  • the average surface roughness Ra of a part of the plate is at most 0.3 ⁇ m, in particular at most 0.2 ⁇ m and particularly preferably at most 0.1 ⁇ m. At least 40%, in particular at least 48%, of the surface preferably show these values.
  • the average surface roughness Ra can be determined in accordance with DIN 4768 using a Talysurf 50 measuring device from Taylor Hobson.
  • the surface roughness Ra of the plate is generally influenced by varying various parameters, which depend on the type of manufacture.
  • the temperature of the melt during extrusion is one of the factors, with a lower temperature of the melt resulting in a smoother surface.
  • the temperature of the melt depends on the exact composition of the molding compound.
  • the temperature of the melt is generally in the range from 150 to 300 ° C., preferably in the range from 200 to 290 ° C. These temperatures refer to the temperatures of the melt at the nozzle outlet.
  • the surface roughness can be influenced via the gap between the rollers used to smooth the plates.
  • a calender comprises, for example, 3 rolls in an L arrangement, the molding compound being guided from the nozzle onto the nip between roll 1 and roll 2 and looping around the roll 2 by 60-180 °, the gap between roll 2 and roll 3 smoothes the surfaces. If the gap between roller 2 and roller 3 is set to plate thickness, the scattering particles on the plate surface are pressed into the matrix, as a result of which the surface is smoother.
  • the shaped body in particular if it is not colored, has a Tau D65 / 10 ° transmittance according to DIN 5036 greater than or equal to 30%, in particular greater than or equal to 60% and particularly preferably greater than or equal to 70%. Colored moldings generally have correspondingly lower values for the degree of transmission.
  • the molded body can be colored. Dyes and / or soot known per se are particularly suitable for coloring.
  • Particularly preferred dyes are commercially available. These include, among others, ⁇ Sandoplast Rot G and ⁇ Sandoplast Gelb 2G each from Clariant and ⁇ Macrolex Grün 5B and ⁇ Macrolex Violett 3R each from Bayer.
  • the molded body can known soluble fluorescent dyes, for. B. contain those based on the chemical class of perylenes.
  • fluorescent dyes may be mixtures of N, N '-disubstituatorm 3,4: 9, IO-perylenebis (dicarboximide) and yellow fluorescent dyes with defined color coordinate ranges in accordance with the CIE 1931 standard colorimetric system, and fluorescence / luminescence factors greater 5 act.
  • fluorescent dyes which in plastics such. B.
  • polycarbonate, polymethyl methacrylate, polyvinylidene fluoride or mixtures of polymethyl methacrylate and polyvinylidene fluoride are soluble and suitable for yellow fluorescent articles or moldings are described in WO 99/16847, among others.
  • the combination of fluorescent dyes with other colorants enables the coverage of a larger color spectrum.
  • a yellow fluorescent fluorescent dye with a green pigment e.g. B, copper phthalocyanine green
  • a blue pigment e.g. B, copper phthalocyanine green
  • Lumogen® F Orange 240 The commercially available fluorescent dyes Lumogen® F Orange 240, Lumogen® F Yellow 083, Lumogen® F Red 300 (Lumogen®: brand of BASF AG, Ludwigshafen, Germany) and Hostasol® Yellow 3G are particularly suitable for the purposes of the invention.
  • concentration of these dyes depends on the desired color impression and the thickness of the plate. Without being restricted thereby, this concentration per dye is generally in the range from 0 to 0.8% by weight, preferably 0.000001 to 0.4% by weight, based on the total weight of the colored shaped bodies.
  • the sum of the dye concentrations is preferably in the range from 0 to 1% by weight, preferably 0.0001 to 0.8% by weight and particularly preferably 0.01 to 0.5, based on the total weight of the colored moldings.
  • the shaped bodies of the present invention can have pigments.
  • white pigments which have a refractive index difference of + 0.4 to 1.5, preferably from + 0.5 to 1.4, particularly preferably from 1.0 to 1.3 to the plastic matrix and in the plastic matrix may be contained in a concentration of 0.001 to 0.1, preferably 0.005 to 0.01% by weight.
  • Preferred white pigments are e.g. B. titanium dioxide (TiO 2 ), zinc oxide (ZnO) or zinc sulfide (ZnS).
  • the molded body preferably has a yellowness index D65 / 10 0 according to DIN 6167 less than or equal to 12, in particular less than or equal to 10, without this being intended to impose a restriction.
  • the moldings of the present invention can be thermoformed excellently without the gloss of the surface or the yellowness index of the molding being adversely affected thereby.
  • the shaping is known to the person skilled in the art.
  • the molded body is heated and shaped using a suitable template.
  • the temperature at which the forming takes place depends on the softening temperature of the substrate from which the plastic body was made.
  • the other parameters, such as the forming speed and forming force, are also dependent on the plastic, these parameters being known to the person skilled in the art.
  • bending forming processes are particularly preferred. Such methods are used in particular for processing cast glass. More detailed information can be found in "Acrylic glass and polycarbonate correct machining and processing" by H.Kaufmann et al.
  • a special embodiment of the molded body of the present invention has an intensity half-value angle greater than or equal to 15 °, in particular greater than or equal to 25 °.
  • the shaped body has a scattering value according to DIN 5036 greater than or equal to 0.15, in particular greater than or equal to 0.35, without this being intended to impose a restriction.
  • the surface of the polymethyl methacrylate plates according to the invention have a glossy appearance in reflection.
  • the characterization can be carried out by measuring the gloss with a reflectometer according to DIN 67530.
  • the gloss of the plates is preferably at an angle of 85 ° of at least 50, particularly preferably of at least 60 and very particularly preferably of at least 70. These values relate to part of the surface of the shaped body, preferably at least 40%, in particular at least 48 % of the surface of the shaped body have these values. It should be noted here that 50% of the surface faces the illuminant inwards. This part of the surface is therefore not visible from the outside. Accordingly, the outward-facing surface facing away from the illuminant should have the highest possible gloss.
  • a shaped body according to the invention preferably has a length in the range from 25 mm to 10000 mm, preferably from 50 to 3000 mm and particularly preferably from 200 to 2000 mm.
  • the width of this particular embodiment is generally in the range from 25 to 10000 mm, preferably from 50 to 3000 mm and particularly preferably from 200 to 2000 mm.
  • the molded body has a particularly high weather resistance in accordance with DIN EN ISO 4892, Part 2 - weathering or irradiating artificially in devices, filtered xenon arc radiation.
  • the plastic bodies according to the invention are generally very resistant to weathering.
  • the weather resistance according to DIN 53387 (Xenotest) is at least 5000 hours.
  • moldings can have an impact strength according to ISO 179/1 of at least 10 kJ / m 2 , preferably at least 15 kJ / m 2 .
  • the molded body preferably has a modulus of elasticity according to ISO 527-2 of at least 1000 MPa, in particular at least 1500 MPa, without this being intended to impose a restriction.
  • a molded body according to the invention was produced in a casting chamber process.
  • 1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 2 parts by weight of tech polymer SBX 8 were added to 1000 parts by weight of prepolymerized methyl methacrylate (viscosity approx. 1000 mPa * S).
  • a paste was dissolved in this mixture, which comprises 3 parts by weight of a polymethacrylate resin soluble in methyl methacrylate, 7.5 parts by weight of BaSO 4 particles of a size of approximately 3.5 ⁇ m and 30 parts by weight of methyl methacrylate.
  • the components of the paste were dispersed with a high-speed disperser.
  • the mixture was stirred vigorously, placed in a 3 mm thick cord spaced silicate glass chamber and polymerized in a water bath at 45 ° C.
  • the final polymerization was carried out in a drying cabinet at 115 ° C.
  • the optical properties of the shaped body were examined, the results being set out in Table 1.
  • the backlight test is carried out in a light box with an incandescent lamp with a clear glass bulb (60 watts). The sample is held at a distance of approx. 5 cm to 50 cm in front of it. If the filament is not visible, the result is marked with + in Table 1. Otherwise, a sign is shown in Table 1.
  • the molded body was heated to 160 ° C. for 10 minutes and shaped to a depth of about 3 to 4 cm under vacuum.
  • the change in surface gloss is also shown in Table 1. If the gloss of the surface is retained, the result is marked with + in Table 1. Otherwise, a sign is shown in Table 1.
  • the transmittance Tau D65 / 10 0 was determined in accordance with DIN 5036.
  • the yellowness index D65 / 10 0 was determined in accordance with DIN 6167.
  • the molded body was then divided and the various parts were subjected to different resistance tests, the results obtained being set out in Table 2. For this purpose, a sample was heated to 180 ° C. for 30 minutes, after which the yellowness index and the transmission were determined. In addition, a Xenotest was carried out for 5000 hours, after which the yellowness index and the transmission were determined.
  • Example 1 is essentially repeated, except that 2 parts by weight of BaSO 4 particles with a size of 3.5 ⁇ m are added.
  • the results obtained according to the methods set out above are also shown in Tables 1 and 2.
  • Example 1 is essentially repeated, but no scattering particles comprising plastic are used.
  • the results obtained according to the methods set out above are also shown in Tables 1 and 2.
  • Example 1 is essentially repeated, but no inorganic scattering particles are used. Instead, 13.3 parts by weight of SBX 8 are added to the mixture. The results obtained according to the methods set out above are also shown in Tables 1 and 2.
  • Example 1 The basic principles of Example 1 are repeated, but no prepolymer is used. Instead, 10 parts by weight of polystyrene are dissolved in 1000 parts by weight of methyl methacrylate. This mixture is then polymerized in a chamber according to Example 1.
  • the examples and comparative examples show that only the mixtures according to the invention lead to a very good property profile. If only inorganic particles are used, a sufficient scattering effect cannot be achieved, so that the backlighting test is not passed. If, on the other hand, larger quantities of plastic particles are used, the surface of the shaped bodies becomes matt after heating. In addition, the degree of transmittance of these moldings drops sharply when irradiated with UV light. Conventional moldings, in which polystyrene is used as a scattering medium, show a very strong increase in the yellowness index and a strong decrease in the transmission when heated. In addition, the UV resistance is also worse than that of moldings according to the invention.

Abstract

La présente invention concerne des corps façonnés pour la publicité lumineuse, qui comprennent une matrice de poly(meth)acrylate, des particules diffusantes contenant de la matière plastique et des particules diffusantes inorganiques. Ces corps façonnés comprennent 0,05 à 0,5 % en poids de particules diffusantes contenant de la matière plastique, d'une taille comprise dans la plage 5-15 ñm, et 0,1 à 3 % en poids de particules diffusantes inorganiques, d'une taille comprise dans la plage 1-7,5 ñm.
EP04716221A 2003-05-23 2004-03-02 Corps faconnes pour la publicite lumineuse et leur procede de production Withdrawn EP1629044A1 (fr)

Applications Claiming Priority (2)

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DE10323789A DE10323789A1 (de) 2003-05-23 2003-05-23 Formkörper für die Lichtwerbung und Verfahren zu deren Herstellung
PCT/EP2004/002062 WO2004104094A1 (fr) 2003-05-23 2004-03-02 Corps faconnes pour la publicite lumineuse et leur procede de production

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EP1629044A1 true EP1629044A1 (fr) 2006-03-01

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US (1) US20060229397A1 (fr)
EP (1) EP1629044A1 (fr)
JP (1) JP2007500271A (fr)
KR (1) KR20060025531A (fr)
CN (1) CN100355828C (fr)
DE (1) DE10323789A1 (fr)
HK (1) HK1087727A1 (fr)
WO (1) WO2004104094A1 (fr)

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DE102005054591A1 (de) * 2005-11-14 2007-05-16 Roehm Gmbh Vorrichtung zur Beleuchtung mit blauen, grünen, gelben oder roten Leuchtdioden
JP5287081B2 (ja) * 2008-09-24 2013-09-11 住友化学株式会社 Ｌｅｄ光源用光拡散板
TWI588199B (zh) * 2012-05-25 2017-06-21 羅門哈斯公司 光擴散聚合物組成物、製造該光擴散聚合物組成物的方法以及由之製得的物品
CN103665690B (zh) * 2012-08-31 2016-03-16 积水化成品工业株式会社 光扩散体
CN104877288B (zh) * 2014-02-27 2017-09-29 积水化成品工业株式会社 光扩散体

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DE3323951A1 (de) * 1983-07-02 1985-01-03 Röhm GmbH, 6100 Darmstadt Acrylatharze als bindemittel fuer farbmittelkonzentrate
JP2512544B2 (ja) * 1989-01-21 1996-07-03 株式会社クラレ 光拡散性合成樹脂
DE4216341A1 (de) * 1992-05-16 1993-11-18 Roehm Gmbh Lichtstreuende Polymethacrylat-Formkörper mit hohen Temperatur- und Wetterechtheitswerten
DE4326521B4 (de) * 1992-08-10 2005-12-22 Bridgestone Corp. Lichtstreuendes Material und Verfahren zu seiner Herstellung
JP3866397B2 (ja) * 1997-12-10 2007-01-10 旭化成ケミカルズ株式会社 光拡散性に優れたアクリル系樹脂板および照明カバー器具
DE10156068A1 (de) * 2001-11-16 2003-05-28 Roehm Gmbh Lichtleitkörper sowie Verfahren zu dessen Herstellung
DE10162360A1 (de) * 2001-12-18 2003-07-03 Roehm Gmbh Beleuchtbare Vorrichtung
US6773787B2 (en) * 2002-05-01 2004-08-10 General Electric Company Light diffusing articles and methods to manufacture thereof

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DE10323789A1 (de) 2004-12-09
CN100355828C (zh) 2007-12-19
CN1753944A (zh) 2006-03-29
WO2004104094A1 (fr) 2004-12-02
US20060229397A1 (en) 2006-10-12
KR20060025531A (ko) 2006-03-21
JP2007500271A (ja) 2007-01-11
HK1087727A1 (en) 2006-10-20

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