EP2115062A1

EP2115062A1 - Molding compound for matt molded polyacrylate bodies

Info

Publication number: EP2115062A1
Application number: EP07822001A
Authority: EP
Inventors: Klaus Schultes; Ursula Golchert; Stefan Nau
Original assignee: Evonik Roehm GmbH
Current assignee: Evonik Roehm GmbH
Priority date: 2007-01-30
Filing date: 2007-10-30
Publication date: 2009-11-11
Also published as: RU2009132414A; WO2008092516A1; TW200902621A; DE102007005432A1; CN101578333A; KR20090111828A; JP2010516875A; CA2676988A1; MX2009007646A; US20100098907A1; JP5156761B2; BRPI0721404A2

Abstract

The invention relates to a molding compound containing, each based on the total weight of the molding compound, A) 49.5% by weight to 99.5% by weight of a polymer matrix, which consists of a (meth)acrylate (co)polymer or a mixture of (meth)acrylate (co)polymers, B) 0.5% by weight to 15.0% by weight of ceramic pearls, the molding compound having a melt volume-flow rate (MVR), measured according to ISO 1133 at 230°C and 3.8 kg, in the range of 0.1 cm<SUP>3</SUP> / 10 min to 5.0 cm<SUP>3</SUP> / 10 min. The molding compound can be used for the production of molded bodies having a velvety matt and preferably rough surface. Said molded bodies are especially suitable as parts of domestic appliances, communications devices, leisure or sports equipment, body parts or parts of body parts in the automotive, shipbuilding or aviation industry, as parts for lightings, signs or symbols, points of sale or sales racks for cosmetic articles, containers, home or office decorations, in furniture, shower doors or office doors, and for parts in the construction industry, as walls, as window frames, seatings, lighting covers, diffusers and for automotive glazing.

Description

MOLDING FOR MATTED POLYACRYLATE FORM BODY

The invention relates to a molding compound for matted molded body and the corresponding moldings and their use.

STATE OF THE ART

Polymethyl methacrylate (PMMA) based molding compounds are used for a wide variety of applications. For this purpose, the masses are usually extruded or injection-molded into moldings. These moldings are characterized by the typical PMMA properties, such as high scratch resistance, weather resistance, heat resistance, excellent mechanical properties, such as tensile modulus and good stress cracking resistance.

The field of use of extruded or co-extruded PMMA moldings is very versatile: extruded or co-extruded sheets are used both for the exterior, especially for automotive components, components, sporting goods surfaces and lamp covers, as well as indoors, especially in the furniture industry, for lighting covers and interior fittings of automobiles.

In addition to extruded or co-extruded PMMA moldings having a transparent, smooth surface, dull and preferably rough surfaces are frequently desired for such applications because of their more pleasant feel and the optical effect. Such a surface is usually realized by the use of molding compositions with incorporated organic or inorganic particles.

However, these modified molding compositions do not exhibit good mechanical properties when using organic matting agents, in particular no satisfactory abrasion resistance. Also, a good one Weathering resistance of the corresponding moldings are often ensured only by the use of large amounts of light stabilizers.

A disadvantage of the processing of common inorganic matting agents, such. As talc, is the complex incorporation into the PMMA molding compound. For example, it is necessary to work with very high shear energies during compounding in order to incorporate the inorganic matting agent uniformly into the molding compound. If no homogeneous distribution of the scattering agent in the molding composition is ensured, this can be seen on the surface of the extruded or co-extruded PMMA molded articles produced therefrom (defects or irregularities, such as, for example, pimples). Furthermore, the other material properties of such moldings are in need of improvement.

WO 02/068519 describes a solid surface material of a matrix, such. As PMMA, and dispersed therein ceramic beads, such as. B. W-410 Zeeospheres ^®. The ceramic beads are provided with a functional coating that reacts with the resin of the matrix and covalently bonds the beads to the matrix. The surface material of WO 02/068519 is characterized by a high flame resistance.

WO 03/054099 relates to an adhesive strip whose uppermost layer comprises a transparent resin and a matting agent, such as e.g. As ceramic beads includes.

WO 97/21536 discloses an extrusion process with which matting agents, such. B. ceramic beads, can bring in a thermoplastic polymer.

US 5,787,655 describes a non-slip film of a thermoplastic polymer into which inorganic beads, such as. B. ceramic beads are incorporated.

US 5,562,981 relates to the construction of a truck semi-trailer. The sidewalls of the semi-trailer include fiber reinforced plastics, in which ceramic beads have been mixed to further strengthen the walls. WO 2005/105377 discloses a composition of a thermoplastic having a processing temperature of at least 280 ⁰ C, superabrasive particles and a filler, such as. B. ceramic beads. The composition is used for the production of abrasive utensils.

TASK AND SOLUTION

The aim of the present invention was to find a molding composition which can be used for the production of moldings with a fine-matte surface. The molding composition should be producible and processable in the simplest possible way, in particular with relatively little energy expenditure. Furthermore, the articles to be produced from the molding material should have the best possible optical and mechanical properties, the highest possible long-term stability and weathering resistance, and the most homogeneous possible matt surface with the lowest possible gloss. In addition, the articles to be produced from the molding composition should preferably have a rough surface.

These and other objects, which can be derived from the above considerations inevitably or arise directly, are solved by a molding compound having all the features of present claim 1. The subclaims referring back to this claim describe particularly expedient embodiments of the molding compound and the other claims particularly relate to advantageous applications of the molding compositions.

By providing a composition which, based in each case on the total weight of the composition,

A) 49.5% to 99.5% by weight of a polymer matrix consisting of a (meth) acrylate (co) polymer or a mixture of (meth) acrylate (co) polymers,

B) 0.5% to 15.0% by weight ceramic beads, includes, where the molding composition has a volume-melt index MVR, measured according to ISO 1133 at 230 ⁰ C and 3.8 kg in the range of 0.1 cm ^3/10 min to 5.0 cm ^3/10 min, it is possible in not readily predictable way to make available a molding composition that is ideal for the production of moldings with feinmattierter surface. In this case, the molding composition can be produced and processed in a comparably simple manner, in particular with relatively little energy expenditure, and also enables the realization of sophisticated part geometries.

At the same time, the articles which can be produced from the molding compound are distinguished by a combination of advantageous properties:

> They have very good optical properties, in particular a comparatively homogeneous matt surface with a very low gloss. This effect was further enhanced by an attractive surface roughness of the moldings.

> They show excellent mechanical properties, in particular very good abrasion resistance, impact strength and notched impact strength, a high modulus of elasticity and high tensile strength, high scratch hardness and a high Vicat softening temperature, as well as a low thermal expansion coefficient.

> The long-term stability and weather resistance of the moldings is also excellent.

EMBODIMENT OF THE INVENTION

Polymer matrix A)

The polymer matrix A) consists of a (meth) acrylate (co) polymer or a mixture of (meth) acrylate (co) polymers.

(Meth) acrylate (co) polymers In a first particularly preferred embodiment of the present invention, the (meth) acrylate (co) polymer of the matrix comprises a homopolymer or copolymer of at least 80.0% by weight of methyl methacrylate and optionally up to 20.0% by weight of others with methyl methacrylate copolymerizable monomers. The (meth) acrylate (co) polymer is suitably 80.0 wt .-% to 100.0 wt .-%, preferably 90.0 wt .-% - 99.5 wt .-%, of free-radically polymerized methyl methacrylate - Units and optionally to 0.0 wt .-% - 20.0 wt .-%, preferably to 0.5 wt .-% - 10.0 wt .-% of further radically polymehsierbaren comonomers, eg. B. C 1 - to C 4 -alkyl (meth) acrylates, in particular methyl acrylate, ethyl acrylate or butyl acrylate. The average molecular weight M _{w of} the matrix is preferably in the range from 90,000 g / mol to 200,000 g / mol, in particular from 95,000 g / mol to 180,000 g / mol.

Preferably, the polymer matrix consists of a (meth) acrylate (co) polymer from 96.0 wt .-% to 100.0 wt .-%, preferably 97.0 wt .-% to 100.0 wt .-%, particularly preferably From 98.0% by weight to 100.0% by weight of methyl methacrylate and from 0.0% by weight to 4.0% by weight, preferably from 0.0% by weight to 3.0% by weight, in particular from 0.0% by weight to 2.0% by weight of methyl acrylate, ethyl acrylate and / or butyl acrylate.

The (meth) acrylate (co) polymers preferably have a solution viscosity in chloroform at 25 ^° C. (ISO 1628 part 6) of 45.0 ml / g to 80.0 ml / g, preferably 50.0 ml / g to 75 , 0 ml / g. This may correspond to a weight average molecular weight M _w ranging from 80,000 to 200,000 (g / mol), preferably from 100,000 to 170,000. The molecular weight M _w can be determined, for example, by gel permeation chromatography or by a scattered light method (see, for example, BHF Mark et al., Encyclopedia of Polymer Science and Engineering, 2nd Edition, Vol. 10, pages 1 et seq., J. Wiley, 1989). ,

The Vicaterweichungstemperatur VET (ISO 306-B50) is preferably at least 100 ⁰ C, more preferably at least 104 ⁰ C, even more preferably 104 ° C to 114 ° C and in particular 105 ⁰ C to 110 ° C. The volume of melt index MVR (ISO 1133, 230 ⁰ C / 3.8 kg) of the polymer is favorably in the range of 0.5 cm ^3/10 min to 5.0 cm ^3/10 min, more preferably in the range of 1, 0 cm ^3/10 min to 2.9 cm ^3/10 min.

Maleic anhydride-containing (meth) acrylate (co) polymers

In a second particularly preferred embodiment of the present invention, the (meth) acrylate (co) polymer of the matrix comprises a copolymer of methyl methacrylate, styrene and maleic anhydride.

The solution viscosity in chloroform at 25 ^° C. (ISO 1628 part 6) is preferably greater than or equal to 65 ml / g, preferably 68 ml / g to 75 ml / g. This may correspond to a molecular weight M _w (weight average) of 130000 g / mol (determination of M _w by gel permeation chromatography with reference to polymethyl methacrylate as calibration standard). The molecular weight M _w can be determined, for example, by gel permeation chromatography or by a scattered light method (see, for example, BHF Mark et al., Encyclopedia of Polymer Science and Engineering, 2nd Edition, Vol. 10, pages 1 et seq., J. Wiley, 1989). ,

The Vicat softening point VSP (ISO 306-B50) is preferably at least 112 ° C, more preferably 114 ° C to 124 ° C, in particular 118 ° C to 122 ⁰ C.

The volume of melt index MVR (ISO 1133, 230 ⁰ C / 3.8 kg) of the polymer is favorably in the range of 0.5 cm ^3/10 min to 5.0 cm ^3/10 min, more preferably in the range of 1, 0 cm ^3/10 min to 2.9 cm ^3/10 min.

Particularly suitable proportions are:

50% by weight to 90% by weight, preferably 70% by weight to 80% by weight

methyl methacrylate, 10% by weight to 20% by weight, preferably 12% by weight to 18% by weight of styrene and 5% by weight to 15% by weight, preferably 8% by weight to 12% by weight maleic anhydride.

Furthermore, the use of polymer blends has proven particularly useful. These preferably comprise d) at least one low molecular weight (meth) acrylate (co) polymer, characterized by a solution viscosity in chloroform at 25 ^° C. (ISO 1628 part 6) of less than or equal to 55 ml / g, preferably less than or equal to 50 ml / g, in particular 45 ml / g to 55 ml / g (This can be a molecular weight M _w (weight average) of 95000 g / mol (determination of M _w means of

Gel permeation chromatography with reference to polymethyl methacrylate as calibration standard), in mixture with e) a higher molecular weight (meth) acrylate (co) polymer, characterized by a solution viscosity in chloroform at 25 ⁰ C (ISO 1628 - Part 6) of greater than or equal to 65 ml / g, preferably 68 ml / g to 75 ml / g and / or f) another of (d) different (meth) acrylate (co) polymer, characterized by a solution viscosity in chloroform at 25 ⁰ C (ISO 1628 - Part 6) from 50 ml / g to 55 ml / g, preferably from 52 ml / g to 54 ml / g (this may correspond to a molecular weight M _w (weight average) in the range from 80,000 to 200,000 (g / mol), preferably from 100,000 to 150,000) , wherein the components d), e) and / or f) in each case can be understood as individual polymers or as mixtures of polymers, wherein d), e) and / or f) preferably to 100.0 wt. Add% and wherein the polymer mixture d), e) and / or f) nor conventional addition, auxiliary and / or Fü may contain.

Particularly preferred are the following proportions:

Component d): preferably 25.0% by weight to 75.0% by weight, preferably 40.0

Wt .-% to 60.0 wt .-%, in particular 45.0 wt .-% to 55.0 wt .-%. Component e) and / or f): 10.0 wt .-% to 50.0 wt .-%, preferably 12.0 wt .-% to 40.0 wt .-%.

The components d) and e) expediently in each case a copolymer of methyl methacrylate, styrene and maleic anhydride.

Particularly suitable proportions are:

50% by weight to 90% by weight, preferably 70% by weight to 80% by weight

methyl methacrylate,

10 wt .-% to 20 wt .-%, preferably 12 wt .-% to 18 wt .-% of styrene and

5% by weight to 15% by weight, preferably 8% by weight to 12% by weight

Maleic anhydride.

Component f) is preferably a homopolymer or copolymer of at least 80% by weight of methyl methacrylate and optionally up to 20% by weight of further monomers copolymerizable with methyl methacrylate.

The component f) is expediently to 80.0 wt .-% to 100.0% by weight, preferably to 90.0 wt .-% - 99.5 wt .-%, of free-radically polymerized methyl methacrylate units and optionally to 0.0 wt .-% - 20.0 wt .-%, preferably to 0.5 wt .-% - 10 wt .-% of other free-radically polymerizable comonomers, eg. B. C 1 - to C 4 -alkyl (meth) acrylates, in particular methyl acrylate, ethyl acrylate or butyl acrylate. Preferably, the average molecular weight M _{w of} the matrix is in the range from 90,000 g / mol to 200,000 g / mol, in particular 100,000 g / mol to 150,000 g / mol.

Component f) is preferably a copolymer of 95.0% by weight to 99.5% by weight of methyl methacrylate and 0.5% by weight to 5.0% by weight, preferably 1.0% by weight. to 4.0% by weight of methyl acrylate.

The component f) preferably has a Vicaterweichungstemperatur VET (ISO 306-B50) of at least 107 ⁰ C, more preferably from 108 ⁰ C to 114 ° C on. The volume of melt index MVR (ISO 1133, 230 ⁰ C / 3.8 kg) is preferably greater than / equal to 2.5 cm ^3/10 min.

The abovementioned copolymers can be obtained in a manner known per se by free-radical polymerization. EP-A 264 590 describes, for. Example, a method for producing a molding composition from a monomer mixture of methyl methacrylate, vinyl aromatic, maleic anhydride and optionally from a lower alkyl acrylate, wherein the polymerization is carried out to a conversion of 50% in the presence or absence of a non-polymerizable organic solvent and in which the polymerization is continued from a conversion of at least 50% in the temperature range from 75 ° C to 150 ⁰ C in the presence of an organic solvent to a conversion of at least 80% and then the low molecular weight volatiles are evaporated.

In JP-A 60-147 417 a process for the preparation of a highly thermally stable polymethacrylate molding composition is described in which a monomer mixture of methyl methacrylate, maleic anhydride and at least one vinyl aromatic in a polymerization reactor, which is suitable for solution or bulk polymerization, at a temperature of 100 ⁰ C to 180 ⁰ C is fed and polymehsiert. DE-OS 44 40 219 describes a further production process.

The component A) may, for. Example, be prepared by a monomer mixture of 3000 g of methyl methacrylate, 600 g of styrene and 400 g of maleic anhydride with 1.68 g of dilauroyl peroxide and 0.4 g of tert-Butylpehsononanoat as a polymerization initiator, 6.7 g of 2-mercaptoethanol as a molecular weight regulator, and g of 2- (2-hydroxy-5-methylphenyl) benzotriazole is added as UV absorber and 4 g of palmitic acid as mold release agent.

The resulting mixture is placed in a polymerization chamber and degassed for 10 minutes. Thereafter, the water bath for 6 hours at 60 ⁰ C and 25 hours polymerized at 50 ⁰ C water bath temperature. After about 25 hours, the polymerization mixture reaches its maximum temperature at 144 ° C. After removal of the Polymehsationskammer the polymer is annealed for 12 hours at 120 ⁰ C in an air cabinet.

The resulting copolymer is clear and has a yellowness value according to DIN 6167 (D65 / 10 ⁰ ) of 1.4 on an 8 mm thick press plate and a light transmission TD65 according to DIN 5033/5036 of 90.9%. The Vicat softening temperature VET of the copolymehseate is ISO according to ISO306-B50 121 ⁰ C, the reduced viscosity nsp / c 65 ml / g corresponding to an average molecular weight M _w of about 130,000 daltons (based on a polymethyl methacrylate standard).

The component d) may, for. Example, be prepared by reacting a monomer mixture of z. B. 6355 g of methyl methacrylate, 1271 g of styrene and 847 g of maleic anhydride with 1, 9 g of tert-Butylperneodecanoat and 0.85 g of tert-butyl peroxy-3,5,5-trimethylhexanoate as a polymerization initiator and 19.6 g of 2-mercaptoethanol Molecular weight regulator and added to 4.3 g of palmitic acid. The resulting mixture can be filled in a polymerization chamber and z. B. degassed for 10 minutes. Thereafter, in a water bath z. B. 6 hours at 60 ⁰ C, then polymerized for 30 hours at 55 ° C water bath temperature. After about 30 hours, the polymerization mixture reaches its maximum temperature at about 126 ° C. After removal of the polymerization from the water bath, the polymer is in accordance with the component a) in the polymerization for about 7 hours z. B. annealed at 117 ° C in a cupboard.

Matting B): ceramic beads

The molding composition of the invention further contains 0.5 wt .-% to 15.0 wt .-% ceramic beads. Ceramics refer largely to inorganic, fine-grained raw materials formed with water at room temperature and then dried objects, which in a subsequent firing process sintered above 900 ⁰ C to hard, durable objects. The term also includes materials based on metal oxides. Furthermore, fiber-reinforced ceramic materials, such as. B. silicon carbide ceramics z. B. from silicon-containing organic polymers (polycarbosilanes) can be prepared as a starting material, the group of ceramics used in the invention.

The ceramic beads are expediently not covalently bonded to the polymer matrix and can in principle by physical separation methods, such as. B. extraction method with suitable solvents, such. As tetrahydrofuran (THF) are separated from the polymer matrix.

Furthermore, the ceramic beads preferably have a spherical shape, with small deviations from the perfect spherical shape can occur naturally.

The ceramic beads expediently have a diameter in the range of 1 to 200 .mu.m. The average diameter (median value D ₅₀ ) of the ceramic beads is preferably in the range of 1, 0 .mu.m to 15.0 .mu.m. The D95 value is preferably less than or equal to 35 μm, more preferably less than or equal to 13 μm. The maximum diameter of the beads is preferably less than or equal to 40 microns, more preferably less than or equal to 13 microns. The particle size of the beads is preferably determined by sieve analysis.

The density of the ceramic beads is favorably in the range of 2.1 g / cm ³ to 2.5 g / cm ³ .

The concrete composition of the ceramic beads is of minor importance to the present invention. Preferred beads contain, in each case based on their total weight,

55.0 wt.% To 62.0 wt.% SiO 2, more preferably non-crystalline

SiO ₂ , 21, 0 wt .-% to 35.0 wt .-% Al ₂ O ₃ , up to 7.0 wt .-% Fe ₂ O ₃ , up to 11, 0 wt .-% Na ₂ O and up to 6 , 0 wt .-% K ₂ O.

The surface of the ceramic beads, measured by BET nitrogen adsorption method, is preferably in the range of 0.8 m ² / g to 2.5 m ² / g.

Furthermore, it has proven particularly useful for the purposes of the present invention to use such ceramic beads that are hollow inside. In this case, the ceramic beads preferably have a compressive strength such that more than 90% of the beads can not be destroyed by applying a pressure of 410 MPa.

Very particularly suitable in the context of the present invention, ceramic beads include the Zeeospheres ^® by the company, 3M Germany, in particular the type W-210, W-410, G-200 and G-400th

Impact modifier C)

The molding composition according to the invention preferably contains an impact modifier, more preferably an impact modifier based on crosslinked poly (meth) acrylates. The impact modifier is preferably not covalently bound to the polymer matrix A). Preferably, component C) has a two- or three-shell structure.

Particularly preferred impact modifiers are polymerizate particles which have a two-layer, particularly preferably a three-layer core-shell structure and can be obtained by emulsion polymerization (see, for example, US Pat. EP-A 0 113 924, EP-A 0 522 351, EP-A 0 465 049 and EP-A 0 683 028). Typical particle sizes of these emulsion polymers are in the range of 100 nm - 500 nm, preferably 200 nm - 450 nm.

A three-layer or three-phase structure with a core and two shells can be designed in particular as follows. An innermost (hard) shell may, for. B is substantially methyl methacrylate, small amounts of comonomers, such as. For example, ethyl acrylate and a crosslinker, z. As allyl methacrylate, exist. The middle (soft) shell can z. B. from butyl acrylate and optionally styrene and a crosslinker, z. As allyl methacrylate, be constructed, while the outermost (hard) shell substantially corresponds to the matrix polymer, whereby the compatibility and good binding to the matrix is effected. The polybutyl acrylate content of the impact modifier is critical to the impact strength and is preferably in the range of 20.0 wt% to 40.0 wt%, more preferably in the range of 25.0 wt% to 40.0 wt .-%.

Other for the purposes of the present invention particularly suitable impact-modified polymethacrylate molding compositions are, for. In EP-A 0 113 924, EP-A 0 522 351, EP-A 0 465 049 EP-A 0 683 028 and US 3,793,402. A very suitable commercially available product is z. B. METABLEN® IR 441 Fa Mitsubishi Rayon.

In the molding composition are suitably from 5.0 wt .-% to 50.0 wt .-%, preferably 10.0 wt .-% to 20.0 wt .-%, particularly preferably 10.0 wt .-% to 15, 0 wt .-% of an impact modifier which is an elastomeric phase of crosslinked Polymerisatteilchen included. The impact modifier is obtained in a manner known per se by bead polymerization or by emulsion polymerization.

Within the scope of a further particularly preferred embodiment of the present invention, the impact modifier is crosslinked particles having a middle content obtainable by means of bead polymerization Particle size in the range of 50 microns to 500 microns, preferably 80 microns to 120 microns. These usually consist of at least 40.0 wt .-%, preferably 50.0 wt .-% - 70.0 wt .-% of methyl methacrylate, 20.0 wt .-% to 40.0 wt .-%, preferably 25.0 wt .-% to 35.0 wt .-% butyl acrylate and 0.1 wt .-% to 2.0 wt .-%, preferably 0.5 wt .-% to 1, 0 wt .-% of a crosslinking monomers, e.g. B. a polyfunctional (meth) acrylate such. B. allyl methacrylate and optionally other monomers such. Example, 0.0 wt .-% to 10.0 wt .-%, preferably 0.5 wt .-% to 8.0 wt .-% of Ci-C ₄ alkyl (meth) acrylates, such as ethyl acrylate or butyl acrylate , preferably methyl acrylate, or other vinylically polymehsierbaren monomers such as. Styrene.

Usual additives, auxiliaries and / or fillers

The molding composition according to the invention can still conventional additives, auxiliaries and / or fillers, such as. B. thermal stabilizers, UV stabilizers, UV absorbers, antioxidants, in particular soluble or insoluble dyes or colorants.

UV stabilizers and radical scavengers

Optional UV protectants are z. As derivatives of benzophenone, whose substituents such as hydroxyl and / or alkoxy groups are usually in the 2- and / or 4-position. These include 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4, 4'-dimethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone. Furthermore, substituted benzothiazoles are very suitable as UV protection additive, including especially 2- (2-hydroxy-5-methylphenyl) - benzotriazole, 2- [2-hydroxy-3,5-di- (alpha, alpha-dimethyl -benzyl) -phenyl] -benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -benzotriazole, 2- (2-hydroxy-3, 5-butyl-5-methylphenyl) -5-chlorobenzthazole , 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) -benzotriazole, 2- (2-hydroxybenzoyl) 5-t butylphenyl) -benzotriazole, 2- (2-hydroxy-3-sec-butyl-5-t-butylphenyl) -benzotriazole and 2- (2-hydroxy-5-t-octylphenyl) -benzotriazole.

UV protectants which can also be used are 2-cyano-3,3-diphenylacrylic acid ethyl ester, 2-ethoxy-2'-ethyl-oxalic acid bisanilide, 2-ethoxy-5-t-butyl-2'-ethyl-oxalic acid bisanilide and substituted phenyl benzoate.

The UV protectants can be present as low molecular weight compounds, as indicated above, in the polymethacrylate compositions to be stabilized. But it can also UV-absorbing groups in the matrix polymer molecules covalently after copolymerization with polymerizable UV absorption compounds, such as. As acrylic, methacrylic or allyl derivatives of benzophenone or Benzthazoldehvaten be bound.

The proportion of UV protection agents, which may also be mixtures of chemically different UV protection agents, is generally 0.01% by weight to 1.0% by weight, especially 0.01% by weight to 0 , 5 wt .-%, in particular 0.02 wt .-% to 0.2 wt .-% based on the totality of all constituents of Polymethacrylatharzes invention.

As an example of radical scavengers / UV stabilizers here are hindered amines, which are known under the name HALS (JHindered Amine Light Stabilizer) are called. They can be used for the inhibition of aging processes in paints and plastics, in particular in polyolefin plastics (Kunststoffe, 74 (1984) 10, pp. 620 to 623; Paint + Varnish, 96 Volume, 9/1990, pp. 689 to 693 ). The stabilizing effect of the HALS compounds is due to the tetramethylpiperidine group contained therein. This class of compounds may be both unsubstituted and substituted with alkyl or acyl groups on the piperidine atom. The sterically hindered amines do not absorb in the UV range. They catch formed radicals, which the UV absorbers can not do. Examples of stabilizing HALS compounds which can also be used as mixtures are:

Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro (4,5) decane-2,5-dione, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, poly (N-β-hydroxyethyl-2,2,6,6-tetramethyl-4-) hydroxy-piperidine-succinic acid ester) or bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate.

The radical scavengers / UV stabilizers are used in the molding compositions according to the invention in amounts of 0.01% by weight to 1.5% by weight, in particular in amounts of 0.02% by weight to 1.0% by weight. %, in particular in amounts of 0.02 wt .-% to 0.5 wt .-% based on the totality of all components.

Lubricant or mold release agent

Lubricants or mold release agents are of particular importance for the injection molding process, which can reduce or completely prevent possible adhesion of the molding compound to the injection mold.

As adjuvants can therefore lubricants, for. B. selected from the group of saturated fatty acids having less than C ₂ o, preferably Ci ₆ to Ci ₈ carbon atoms or the saturated fatty alcohols containing less than C20, preferably C16 to C18 carbon atoms. Preference is given to small amounts of at most 0.25 wt .-%, z. B. 0.05 wt .-% to 0.2 wt .-%, based on the molding composition.

Suitable z. As stearic acid, palmitic acid, technical mixtures of stearic and palmitic acid. Further suitable z. As n-hexadecanol, n-octadecanol, and technical mixtures of n-hexadecanol and n-octadecanol.

A particularly preferred slip-release agent is stearyl alcohol. Volume melt index MVR of the molding compound

In the present invention, the molding composition a volume melt index MVR, measured according to ISO 1133 at 230 ⁰ C and 3.8 kg in the range of 0.1 cm ^3/10 min to 5.0 cm ^3/10 min. Here, the MVR is measured according to ISO 1133 at 230 ⁰ C and 3.8 kg, preferably at least 0.2 cm ^3/10 min, more preferably at least 0.3 cm ^3/10 min, suitably at least 0.4 cm ³ / 10 min, in particular at least 0.5 cm ^3/10 min. Further, the MVR, measured according to ISO 1133 at 230 ° C and 3.8 kg, preferably less than 3.5 cm ^3/10 min, more preferably less than 3.0 cm ^3/10 min, advantageously less than 1, 5 cm ³ / 10 min, most preferably less than 1, 4 cm ^3/10 min, especially less than 1, 1 cm ^3/10 min and most preferably less than 0.9 cm ^3/10 min. For molding compositions having impact modifier is the MVR, measured according to ISO 1133 at 230 ⁰ C and 3.8 kg, preferably in the range of 0.1 cm ^3/10 min to 3.0 cm ^3/10 min. For molding compositions without impact modifier is the MVR, measured according to ISO 1133 at 230 ° C and 3.8 kg, preferably in the range of 0.5 cm ^3/10 min to 5.0 cm ^3/10 min.

Production of the molding composition according to the invention

The molding composition according to the invention can be prepared by dry blending the components, which may be in the form of powders, granules or preferably granules. Furthermore, it can also be prepared by melting and blending the polymer matrix and optionally the toughening modifier in the melt state or by melting dry premixes of individual components and adding the ceramic beads. This can be z. B. in single or twin-screw extruders. The resulting extrudate can then be granulated. Usual additives, auxiliaries and / or fillers can be added directly or added later by the end user as needed. Processing into moldings

The molding composition of the invention is suitable as a starting material for the production of moldings with samtmatter and preferably rough surface. The transformation of the molding composition can be known per se, for. B. by processing over the elastoviskosen state, d. H. by kneading, rolling, calendering, extruding or injection molding, wherein extrusion and injection molding, in particular extrusion, are preferred in the present case.

The injection molding of the molding composition can be carried out in known manner at temperatures in the range of 220 ⁰ C - 260 ⁰ C (melt temperature) and a mold temperature of preferably 60 ° C to 90 ⁰ C. When using tools with mold cavities with smooth or mirror-smooth inner surfaces (cavities) matted moldings are obtained. When using tools with mold cavities with rough inner surfaces (cavities) even more frosted moldings are obtained.

The extrusion is preferably carried out at a temperature of 220 ° C to 260 ° C.

moldings

The moldings obtainable in this way are preferably characterized by the following properties:

The roughness value R _z according to DIN 4768 is expediently greater than or equal to 0.3 μm, preferably at least 0.7 μm, particularly preferably between 2.5 μm and 20.0 μm. The degree of gloss (R 60 °) according to DIN 67530 (01/1982) is preferably at most 45%, particularly preferably at most 38%. The transmission according to DIN 5036 is preferably in the range of 40% to 93%, particularly preferred in the range of 55% to 93%, in particular in the range of 55% to 85%. The intensity half-value angle according to DIN 5036 is preferably in the range of 1 ° to 55 °, more preferably in the range of 2 ° to 40 °, in particular in the range of 8 ° to 37 °.

In a first particularly preferred embodiment of the present invention, the Vicaterweichungstemperatur VET (ISO 306-B50) of the molding is preferably at least 90 ⁰ C, more preferably at least 95 ° C, most preferably at least 100 ⁰ C and is suitably between 90 ⁰ C and 170 ⁰ C, in particular between 102 ° C and 130 ° C. Furthermore, the shaped body preferably has one or more, more preferably as many as possible, of the following properties:

I. a breaking stress according to ISO 527 (5 mm / min) of at least 50 MPa, in particular in the range of 65 MPa to 90 MPa,

II. An E-module according to ISO 527 greater than 3200 MPa,

III. an impact strength according to ISO 179/1 eil greater 20 KJ / m ² and

IV. A coefficient of linear expansion to ISO 11359 smaller 8 * 10 ^"5 / ° K, more preferably less than 7.1 * 10 ^{" 5} / ° K.

Such moldings are usually obtained from molding compositions containing no impact modifier.

In a second particularly preferred embodiment of the present invention, the Vicaterweichungstemperatur VET (ISO 306-B50) of the molding is preferably at least 90 ⁰ C, more preferably at least 95 ° C and is suitably between 90 ⁰ C and 170 ° C, in particular between 95 ° C and 110 ^° C. Furthermore, the shaped body preferably has one or more, particularly preferably as many, of the following properties:

I. a yield stress according to ISO 527 (50 mm / min) of at least 30 MPa, in particular in the range of 34 MPa to 50 MPa,

II. An E-module according to ISO 527 greater than 1400 MPa, I. a notched impact strength according to ISO 179/1 eil greater 4 KJ / m ² and

IV. A coefficient of linear expansion to ISO 11359 less than 12 * 10, -5 // ⁰ K.

Such moldings are usually obtained from molding compositions containing at least one impact modifier.

uses

The moldings according to the invention can be used, in particular, as parts of household appliances, communication devices, hobby or sports equipment, body parts or parts of body parts in automobile, ship or aircraft construction, as parts for lighting, signs or symbols, outlets or cosmetics sales stands, containers, home or office decorations , Furniture applications, shower doors and office doors, and as parts, in particular panels, used in the construction industry, as walls, in particular as noise barriers, as window frames, benches, lighting covers, diffusers and automotive glazing. Typical automobile exterior parts are z. As spoilers, panels, roof modules or exterior mirror housing.

EXAMPLES

In the following the invention will be explained in more detail by examples, without this being intended to limit the inventive concept.

As a polymer matrix PLEXIGLAS ^® 7H, PLEXIGLAS ^® 8N, PLEXIGLAS ^® zk6BR and PLEX ^® 8908F of the company. Roehm GmbH was used.

As ceramic beads, the products Zeeospheres W-210, W-410, G-200 and G-400 of the company. 3M Germany GmbH were used.

The individual components were mixed by means of single-screw extruders. The compositions of the individual examples are documented in Table 1. The volume flow index MVR (test standard ISO 1133: 1997) and the density of the molding compositions was determined.

Test specimens were produced by injection molding and ribbon extrusion from the blended molding compositions. During processing, metal abrasion was not detected in either tape extrusion or injection molding. The corresponding test pieces were tested according to the following methods:

Molded Vicat (16h / 80 ° C): Determination of Vicat

Softening temperature (test standard DIN

ISO 306: August 1994)

KSZ (Charpy i 79/1 eU): determination of the charpy

Notched impact strength (test standard: ISO 179:

1993)

SZ (Charpy 179/1 eil): Determination of Charpy impact strength

(Test standard: ISO 179: 1993)

E-modulus: determination of modulus of elasticity (test standard:

ISO 527-2)

Tensile strength: Determination of breaking stress

(Test standard: ISO 527, 5 mm / min), the

Yield stress (test standard: ISO 527, 50 mm / min) and / or elongation at break

(Test standard: ISO 527, 50 mm / min)

Transmission (T): according to DIN 5036 Intensity half-value angle (IHW): measured according to DIN 5036 with one

LMT goniometer measuring station GO-T-1500 of the company LMT

Coefficient of linear expansion: ISO 1 1359 (0 ⁰ C - 50 ⁰ C)

Scratch hardness: according to Erichsen 413

Scratch Hardness ribbon:

Surface Roughness: Roughness Ra, Rz and Rt according to DIN

4768. Ra values <2 μm were determined with a cut-off of 0.8 mm, with Ra> 2 μm with a cut-off of 2.5 mm. The roughness measurements were carried out using a Form Talysurf 50, manufacturer is the Rank Taylor Hobson GmbH.

Gloss: Gloss measurement according to DIN 67530

(01/1982): "Reflectometer as aid for gloss evaluation on flat paint and plastic surfaces"

The results of the tests on the blends and the corresponding moldings can be seen in Table 2. It can be clearly seen the improvements which are achieved by the present invention:

Through the use of ceramic beads as a matting can be extruded from the corresponding molding compositions tapes, which have a lower gloss and a uniform feinmattierte surface and an attractive surface roughness. Furthermore, an improved scattering effect, a decrease in the expansion coefficient, and an improvement in mechanical properties such as impact resistance, notched impact strength, Young's modulus, and scratch resistance are observed.

D ₅₀ : 3 μm, D ₉₅ : 12 μm; 24 μm, ^ά : D ₅₀ : 4 μm, D ₉₅ : 12 μm,

4. D 50-5 μm, D ₉₅ : 24 μm

Table 1 (continued): Composition of the molding compositions

Table 2: Properties of the molding compounds / moldings

κ>

ul

Table 2 (continued) zk6BR B15 B16 B17 PLEX B1 i B19 B20

8908F

MVR [cm ³ / 10min] 1, 5 1, 5 1, 4 1, 3 0.3 0.2 0.2 0.1

Vicat [ ⁰ C] 98 98 98 98 89 90 91 91

Ra [μm] 0.1 0.2 0.4 0.4 0.2 0.3 0.5 0.7

Rz [μm] 0.9 1, 6 3.0 3.4 1, 9 2.5 3.8 5.1

Rt [μm] 0.2 3.1 5.7 5.9 3.3 3.9 5.2 7.2

SZ [kJ / m ² ] κ>

KSZ [kJ / m ² ] 7.2 6.4 5.1 4.8 9.8 6.7 6.4 5

Yield stress (50 mm / min) 46 46 46 46 37 37 36 37

[MPa]

Elongation at break (50 mm / min) 5.4 5.1 4.7 4.5 4.8 4.9 4.7 4.5

Modulus of elasticity (1 mm / min) [MPa] 1760 1800 1870 1990 1510 1500 1570 1670

Linear expansion coefficient 9.6 9.7 9.5 9.1 1, 1 1, 2 1, 1 1, 0

[10 ^"5 / K]

Scratch Hardness FB 2B 4B B 2B 4B 6B

Table 2 (2nd continuation)

κ>

Table 2 (3rd sequel) zk6BR B15 B16 B17 PLEX 8908 B18 B19 B20

Shine r / oi

R (20 °) 12 10 5 4 R (60 °) 60 55 37 32 R (85 °) 91 87 63 57

κ>

Claims

claims:

1. molding composition comprising, in each case based on the total weight of the molding material,

B) 0.5 wt .-% to 15.0 wt .-% ceramic beads, characterized in that the molding material has a volume melt index MVR, measured according to ISO 1133 at 230 ⁰ C and 3.8 kg, of 0.1 cm ^3/10 min to 5.0 ^cm3 / 10 min.

2. Molding composition according to claim 1, characterized in that the ceramic beads are not covalently bonded to the polymer matrix.

3. Molding composition according to claim 1 or 2, characterized in that the ceramic beads have an average diameter, measured as D ₅ o value, in the range of 1, 0 microns to 15.0 microns.

4. Molding composition according to at least one of the preceding claims, characterized in that the ceramic beads have an average diameter, measured as D ₉₅ value, in the range of 3 microns to 35 microns.

5. Molding composition according to at least one of the preceding claims, characterized in that the ceramic beads have a density in the range of 2.1 g / cm ³ to 2.5 g / cm ³ .

6. Molding composition according to at least one of the preceding claims, characterized in that the ceramic beads, in each case based on their total weight,

55.0 wt% to 62.0 wt% SiO ₂ , 21, 0 wt% to 35.0 wt% Al ₂ O ₃ , up to 7.0% by weight of Fe ₂ O ₃ , up to 11.0% by weight of Na ₂ O and up to 6.0% by weight of K ₂ O.

7. Molding composition according to at least one of the preceding claims, characterized in that the ceramic beads have a surface, measured by BET nitrogen adsorption method in the range of 0.8 m ² / g to 2.5 m ² / g.

8. Molding composition according to at least one of the preceding claims, characterized in that the ceramic beads are hollow inside.

9. Molding composition according to at least one of the preceding claims, characterized in that the molding composition, based on its total weight, 0.1 wt .-% to 50.0 wt .-% of at least one impact modifier C), which is not covalent to the polymer matrix is bound.

10. Molding composition according to claim 9, characterized in that the impact modifier C) contains poly (meth) acrylate units.

11. Molding composition according to claim 9 or 10, characterized in that the impact modifier C) has a two- or dreischaligen structure.

12. Molding composition according to at least one of the preceding claims, characterized in that the polymer matrix A) is a (meth) acrylate (co) polymer from 96.0 wt .-% to 100.0 wt .-% of methyl methacrylate and 0.0 to 4 , 0 wt .-% methyl acrylate, ethyl acrylate and / or butyl acrylate.

13. Molding composition according to at least one of the preceding claims, characterized in that the polymer matrix A) comprises a copolymer of methyl methacrylate, styrene and maleic anhydride.

14. Molding composition according to claim 13, characterized in that the polymer matrix A) is a copolymer

From 50 to 90% by weight of methyl methacrylate,

10 to 20 wt .-% of styrene and

5 to 15 wt .-% maleic anhydride.

15. Molding composition according to at least one of the preceding claims, characterized in that the molding composition contains the following components: d) a low molecular weight (meth) acrylate (co) polymer, characterized by a solution viscosity in chloroform at 25 ⁰ C (ISO 1628 - Part 6 ) of less than or equal to 55 ml / g; e) a higher molecular weight (meth) acrylate (co) polymer, characterized by a solution viscosity in chloroform at 25 ^° C. (ISO 1628 part 6) of greater than or equal to 65 ml / g and / or f) another of d) different ( Meth) acrylate (co) polymer, characterized by a solution viscosity in chloroform at 25 ⁰ C (ISO 1628 - Part 6) of 50 to 55 ml / g, wherein the components d), e), and / or f) each individually taken as individual polymers as well as mixtures of polymers can be understood.

16. A molding composition according to one or more of the preceding claims, characterized in that the molding composition has a volume-melt index MVR, measured according to ISO 1133 at 230 ⁰ C and 3.8 kg in the range of 0.1 cm ^3/10 min to 3 , having 0 cm ^3/10 min.

17. A molding composition according to one or more of claims 1 to 15, characterized in that the molding composition has a volume-melt index MVR, measured according to ISO 1133 at 230 ⁰ C and 3.8 kg in the range of 0.5 cm ^3/10 min has to 5.0 cm ^3/10 min.

18. Molding composition according to one or more of the preceding claims, characterized in that a lubricant is contained as adjuvant.

19. A molding composition according to claim 18, characterized in that the lubricant is stearyl alcohol.

20. Molding composition according to one or more of the preceding claims, characterized in that it is in the form of a molding material granules.

21. A process for the production of moldings, characterized in that one transforms a molding composition according to one or more of the preceding claims.

22. The method according to claim 21, characterized in that the molding compound is extruded or injection-molded.

23. Shaped body, producible by a method according to claim 21 or 22.

24. Shaped body according to claim 23, characterized in that it has a roughness value Rz according to DIN 4768 of at least 0.3 microns and a gloss (R 60 °) according to DIN 67530 of at most 45

25. Shaped body according to claim 23, characterized in that it has a transmission according to DIN 5036 in the range of 40% to 93% and an intensity half-value angle according to DIN 5036 in the range of 1 ° to 55 °.

26. Shaped body according to claim 23, 24 or 25, characterized in that it has one or more of the following properties a. a Vicat softening point to ISO 306-B50 of at least 90 ⁰ C, b. a breaking stress according to ISO 527 at 5 mm / min of at least 50 MPa, c. an E-module according to ISO 527 greater than 3200 MPa, d. an impact strength according to ISO 179/1 eil greater than 20 KJ / m ² and e. a coefficient of linear expansion according to ISO 11359 smaller 8 * 10 ^" 5 / ° K ..

Shaped body according to claim 23, 24 or 25, characterized in that it has one or more of the following characteristics a. a Vicat softening point to ISO 306-B50 of at least 90 ⁰ C, b. a yield stress to ISO 527 at 50 mm / min of at least 30 MPa, c. an E-module according to ISO 527 greater than 1400 MPa, d. an impact strength to ISO 179/1 eil greater than 4 kJ / m ² and e. a coefficient of linear expansion to ISO 11359 less than 12 * 10 ^" 5 / ° K.

28. Use of the moldings according to one or more of claims 23 to 27 as parts of household appliances, communication devices, hobby or sports equipment, body parts or parts of body parts in the automotive, ship or aircraft, as parts for lighting, signs or symbols, outlets or cosmetics sales stands, containers, home or office decorations, furniture applications, shower doors and office doors, and as parts in the construction industry, as walls, as window frames, benches, light covers, diffusers and automotive glazing.