DE19956483A1 - Lacquered molded plastic parts, process for their production and their use - Google Patents

Abstract

Lacquered plastic molded part, containing at least one plastic layer (A), the at least one graft copolymer (a1) made of DOLLAR A (a11) at least one rubber-elastic polymer with a glass transition temperature of below 10 ° C. as the graft base DOLLAR A (a12) at least one graft pad made of at least one copolymer with a glass transition temperature above 30 DEG C DOLLAR A or consists thereof; and at least one coating (B) located on the plastic layer (A), producible from a coating which, in the hardened state, has a storage module E 'in the rubber-elastic range of at least 10 · 7.6 · Pa and a loss factor tan delta at 20 ° C. has a maximum of 0.1, the storage module E 'and the loss factor tan delta being measured using dynamic mechanical thermal analysis (DMTA) on free homogeneous films with a layer thickness of 40 + - 10 mum; and a method for producing the plastic molding and its use.

Description

The present invention relates to new painted plastic molded parts. Also concerns the present invention a new process for their preparation. Last but not least concerns Present invention the use of the new painted plastic molded parts for the Manufacture of motor vehicle bodies, in particular automobile bodies.

Plastic moldings, especially large plastic moldings, win because of their easy to manufacture, their comparatively low weight and their excellent application-related property profile that is tailored to the respective Purpose can be customized in the manufacture of Motor vehicle bodies, in particular automobile bodies, are becoming increasingly important. Here it is necessary to use large-scale plastic outer parts in their hardness and To further improve scratch resistance.

Large-scale exterior parts are currently mainly made from blends of polyphenylene ether and Polyamide (PPE / PA) or polybutylene terephthalate and polycarbonate (PBT / PC). While the exterior parts made of PPE / PA are painted online, the exterior parts are made of PBT / PC generally offline, i.e. H. separately, painted.

In order to achieve the high hardness required by the motor vehicle manufacturers, the Plastic parts coated with a scratch-resistant clear coat. Here it is over procedural, ecological and economic reasons that the Crosslink the clearcoats used at room temperature as quickly as possible and thereby if possible, cause no emissions of organic compounds. This can be done with UV Clear lacquers, as described for example in German patent DE-C-197 09 467 will be achieved. These UV clear coats are so-called 100% - Systems that do not contain organic solvents when irradiated with actinic Harden radiation within seconds and deliver highly scratch-resistant coatings.

It is clear from the German patent DE-C-197 09 467 that the known UV Clear varnishes can also be used to coat plastics. However, it will not specifies which plastics are suitable. The in Examples 1 to 4 and lines 40 to 44 of page 3 of the German patent coating of Teflon and polypropylene are only used to produce free films for measurement of the memory module E 'and the loss factor tan δ with the dynamic mechanical Thermal analysis (DMTA), since the films are made from the well-known hardened UV clearcoats these polymers do not adhere, but are easily removed without damage can be.

The ones that have so far been mainly used by motor vehicle manufacturers Plastic molded parts made of PBT / PC have the serious disadvantage that their Toughness, especially at low temperatures, and their elongation at break due to Paintwork can be drastically lowered. This can go so far that the painted Plastic moldings for an outdoor application where they have a strong mechanical Exposure - for example by falling rocks - no longer in Come into consideration. This adverse effect also occurs when using the from the German patent DE-C-197 09 467 known UV clearcoats.

The object of the present invention is to find new painted plastic molded parts, which no longer have the disadvantages of the prior art, but which have the paintwork can be equipped with high scratch resistance without the others being used for the Outdoor application on motor vehicle bodies essential application technology Properties are affected. In addition, the new painted plastic molded parts also have an excellent overall visual impression, excellent weather resistance, moisture resistance and Chemical resistance and excellent adhesion between plastics and Have paint jobs. Last but not least, the clear coat should not delay the Cause hues of colored plastic molded parts.

Accordingly, the new painted plastic molding was found containing

• A) at least one plastic layer, the
  • 1. at least one graft copolymer
    • 1. at least one rubber-elastic polymer with a glass transition temperature of below 10 ° C as a graft base
    • 2. at least one graft pad made of at least one copolymer with a glass transition temperature above 30 ° C
    contains or consists of;
  and
• B) at least one coating located on the plastic layer (A), which can be produced from a coating which, in the cured state, has a storage module E 'in the rubber-elastic range of at least 10 ^7.6 Pa and a loss factor tan δ at 20 ° C. of a maximum of 0.1 The storage module E 'and the loss factor tan δ were measured with dynamic mechanical thermal analysis (DMTA) on free homogeneous films with a layer thickness of 40 ± 10 µm.

In the following, the new painted plastic molded part is called "according to the invention Plastic molding "referred to.

In addition, the new process for the production of a painted plastic molded part containing

• A) at least one plastic layer, the
  • 1. at least one graft copolymer
    • 1. at least one rubber-elastic polymer with a glass transition temperature of below 10 ° C as a graft base
    • 2. at least one graft made of at least one copolymer with a glass transition temperature above 30 ° C.
    contains or consists of;
  and
• B) at least one paint job

by applying at least one lacquer to the surface of the plastic layer (A) and hardening the resulting lacquer layer, which results in the lacquer (B), characterized in that a lacquer is used which, in the hardened state, has a storage module E 'in the rubber-elastic range of at least 10 ^7.6

Pa and has a loss factor tan δ at 20 ° C of at most 0.1, which Storage module E 'and the loss factor tan δ with the dynamic mechanical thermo Analysis (DMTA) on free homogeneous films with a layer thickness of 40 ± 10 µm were measured.

The following is the new process for producing a painted plastic molding referred to as the "inventive method".

Further objects according to the invention are evident from the description.

In view of the prior art, it was surprising and not for the person skilled in the art to be expected that the task underlying the present invention with the help of Plastic molding according to the invention and with the aid of the method according to the invention could be solved. It was particularly surprising that the inventive Plastic molded parts have excellent adhesion between the paint and plastic has and that application properties that are for outdoor use are essential, are not deteriorated by the painting.

The plastic molding according to the invention contains as an essential component of the invention at least one plastic layer (A).  

This means that the plastic molding according to the invention can be a laminate that made up of at least two layers of different material composition is. It is essential here that at least one plastic layer (A) is the outermost layer of the laminate so that it is in direct contact with the paint. The Plastic molded part according to the invention can, however, only consist of a plastic layer (A) exist. Which variant is chosen depends on the one with the respective one Related technical requirements.

The molded plastic part according to the invention is of any external shape. So it can Have the shape of a flat or curved plate, the perforations and / or Can have surface structures. It can also be compact have three-dimensional shape. Examples of such shapes are hubcaps, fenders, Sills, bumpers, bonnets, trunk lids, wind deflectors, spoilers, housings for Screens or telephones, household appliances or furniture.

The plastic layer (A) to be used according to the invention contains at least one Graft copolymer (a1) or consists of this. Which variant is chosen depends on the technical requirements of the respective purpose.

The graft copolymer (a1) to be used according to the invention consists of at least one, in particular one, rubber-elastic polymer (a11) with a Glass transition temperature of below 10 ° C, preferably below 0 ° C, preferably -20 ° C and in particular -25 ° C as a graft base.

Examples of suitable polymers (a11) are natural rubber, synthetic rubber based on conjugated dienes, optionally i. V. m. further copolymers or elastomers based on C ₁ to C ₈ alkyl esters of acrylic acid, which may contain further comonomers.

Polybutadiene (cf. the German Patents DE-A-14 20 775 or DE-A-14 95 089) or the copolymers Polybutadiene and styrene (see British Patent GB-A-649 166) are used.

Further examples of suitable graft bases (a11) are constructed from, in each case based on the graft base (a11),

• 1. 70 to 99.9% by weight, in particular 99% by weight, of at least one C ₁ to C ₈ alkyl ester of acrylic acid, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, in particular n-butyl acrylate;
• 2. 0 to 30% by weight, in particular 0 to 20% by weight, of at least one further hereby copolymerizable monofunctional olefinically unsaturated Monomers such as butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate and / or Vinyl methyl ether; and
• 3. 0.1 to 5% by weight, in particular 1 to 4% by weight, of at least one of them copolymerizable polyfunctional, especially bifunctional or trifunctional, olefinically unsaturated, the crosslinking monomers that are not in the 1,3-position is conjugated, such as divinylbenzene, maleic acid diallyl ester, Fumaric acid diallyl ester, phthalic acid diallyl ester, triallyl isocyanurate or Tricyclodecenyl acrylate, especially tricyclodecenyl acrylate (cf. the German Patent DE-A-12 60 135).

These graft bases are known per se and are used, for example, in the German Patent DE-A-31 49 358 described.

The polymers (a11) or the graft bases (a11) are preferably in the Graft copolymers (a1) in an amount of, based on the Graft copolymer (a1), 40 to 80 wt .-%, preferably 45 to 75 wt .-% and contain in particular 50 to 70 wt .-%.

The graft copolymer (a1) contains at least one further essential constituent a graft (a12) with a glass transition temperature above 30 ° C. Preferably the outermost graft (a12) has a glass transition temperature above 30 ° C, whereby a polymer formed from the monomers of the graft (a12) Glass transition temperature of more than 80 ° C would have.  

Contain suitable grafting pads (a12)

• 1. at least one vinyl aromatic monomer and / or at least one Alkyl (meth) acrylate and
• 2. acrylonitrile, methacrylonitrile, maleic anhydride and / or at least one maleimide N-substituted with C ₁ -C ₈ -alkyl or C ₆ -C ₂₀ -aryl groups

polymerized.

Particularly suitable graft layers (a12) result if the monomers (a121 or a122) styrene or alpha-methylstyrene or mixtures of styrene and acrylonitrile, alpha- Methylstyrene and acrylonitrile, styrene, acrylonitrile and methyl methacrylate or styrene and Maleic anhydride can be used.

Contain particularly suitable grafting pads (a12), each based on the Graft base (a12), 50 to 95 wt .-%, in particular 60 to 80 wt .-%, at least a monomer (a121) and 5 to 50% by weight, in particular 20 to 40% by weight, at least one monomer (a122).

The grafts (a12) can be obtained by copolymerizing the above described monomers (a121) and (a122).

In the event that the graft copolymer (a1) contains a graft base (a11), the is made up of polybutadiene polymers Acrylonitrile-butadiene-styrene graft copolymers or rubbers manufactured by Experts are also referred to as ABS for short.

From a methodological point of view, the graft copolymerization has no special features, but takes place according to the usual and known methods of Graft copolymerization in solution, suspension or, preferably, emulsion as they are is described, for example, in German Patent DE-A-31 49 358.

In the preferred production of ABS in the emulsion or in the solution (solution ABS), the graft base or soft phase (a11) has an average particle diameter (d ₅₀ value of the integral mass distribution) of 0.08 μm. The d ₅₀ value is set in the range from 0.2 to 0.5 μm by enlarging the particles, for example by agglomeration or by obtaining the emulsion by means of the seed latex method. In such graft copolymerizations, the polymerizing monomers (a121) and (a122) are at least partially linked to the already polymerized rubber (a11), the linkage probably occurring at the double bonds contained in the rubber as graft centers.

The grafting can also be done in several stages by first part of the graft envelope or support (a12) forming monomers (a121) and (a122) and then the rest.

In the event that the graft copolymer (a1) contains a graft base (a11) which is composed of elastomers based on C ₁ - to C ₈ -alkyl esters of acrylic acid, one speaks of acrylate-styrene-acrylonitrile graft copolymers or rubbers , which experts also refer to as ASA for short. Their manufacture is known per se and is described, for example, in German patents DE-A-28 26 925, DE-A-31 49 358, DE-A-43 14 118 or DE-A-196 51 350.

The preparation of the graft copolymers (a1) can, for example, according to that in the German patent DE-C-12 60 135 method described. The The graft cover or cover (a12) is constructed in one or two stages.

In the case of the one-stage structure of the graft shell, a mixture of the monomers (a121) and (a122) in the desired weight ratio in the range from 95: 5 to 50:50, preferably 90: 10 to 65:35 in the presence of the elastomer (a11) in itself known manner (cf. the German patent DE-A-28 26 295) preferably in Polymerized emulsion.

In the case of a two-stage construction of the graft shell (a12), the first stage in general 20 to 70 wt .-%, preferably 25 to 50 wt .-%, each based on (a12), from. Only monofunctional ones are preferred for their production vinyl aromatic monomers (a121) used.

The second stage of the graft shell generally makes up 30 to 80% by weight, in particular 50 up to 75% by weight, based in each case on (a12). Mixtures are used to manufacture them from the monomers (a121) and (a122) preferably in a weight ratio (a121): (a122) from 90:10 to 60:40, in particular 80:20 to 70:30.

The conditions of the graft copolymerization are preferably chosen so that particle sizes of 50 to 700 nm (d ₅₀ value of the integral mass distribution) result. Appropriate measures are known and z. B. described in German Patent DE-A-28 26 925.

A coarse-particle rubber dispersion can be applied directly using the seed latex process getting produced.

In order to obtain products that are as tough as possible, a mixture of at least two graft copolymers (a11) with different particle sizes is often used. This can be achieved by the particles of the rubber z. B. be increased by agglomeration, so that the latex is bimodal (d ₅₀ values of the integral mass distribution: 50 to 180 nm and 200 to 700 nm).

The chemical structure of the two graft copolymers (a12) is preferred the same, although the shell of the coarse-particle graft copolymer also has several stages, in particular in two stages.

The graft is in the ABS or ASA (a1) to be used according to the invention. preferably in an amount of, based in each case on (a1), 20 to 60% by weight, preferably 30 to 50 wt .-% included.

The content of ASA or ABS (a1) in the plastic layer (A) can vary widely.

In a first advantageous embodiment, the plastic layer (A) consists of ASA or ABS (a1).

In a second advantageous embodiment, the plastic layer (A) or that contains Mixture of substances (A) that builds up the plastic layer (A), further components. The The lower limit of the ASA or ABS content (a1) then results from the level of Toughness that is still sufficient for a given purpose. The expert can therefore, with the help of his specialist knowledge, the salary, if necessary simple preliminary tests. The proportion of ASA or ABS (a1) is preferably related to the plastic layer (A) or the mixture of substances (A) from which it consists on their total amount, at 1 to 99 wt .-%, preferably 3 to 90 wt .-%, particularly preferably 5 to 80% by weight and in particular 10 to 70% by weight.

Examples of suitable further components are halogen-free thermoplastic Copolymers (a2). If they can be used their share in the Vary the plastic layer (A) widely. The upper limit of the share results from the Level of toughness of the plastic layer (A) for a given Purpose is still sufficient. The upper limit can therefore be easily understood by the person skilled in the art based on his specialist knowledge, possibly with the help of simple preliminary tests be determined. The proportion of (a2) to (A), based on (A), is preferably 5 to 90% by weight, preferably 10 to 85% by weight, particularly preferably 15 to 80% by weight and in particular 20 to 70 wt .-%.

Contain highly suitable copolymers (a2), each based on (a2)

• 1. 50 to 95 wt .-%, preferably 60 to 80 wt .-%, at least one of the above described vinyl aromatic monomers and
• 2. 5 to 50 wt .-%, preferably 20 to 40 wt .-%, at least one of the above described monomers (a122), methyl acrylate and / or methyl methacrylate.

They are resinous, thermoplastic and rubber-free. Particularly preferred Copolymers (a2) are those made from styrene with acrylonitrile and optionally Methyl methacrylate, from alpha-methyl styrene with acrylonitrile and optionally Methyl methacrylate, from styrene and alpha-methyl styrene with acrylonitrile and optionally Methyl methacrylate or from styrene and maleic anhydride.

Such copolymers (a2) are often produced in the production of Graft copolymers (a1) as by-products especially when comparatively large amounts of monomers (a121) and (a122) on comparatively small amounts of graft bases (a11) are grafted on. You can also targeted by radical copolymerization, in particular by emulsion, suspension, Prepare solution or bulk polymerization. They have viscosity numbers in the range from 40 to 160 on what mass average molecular weights of 40,000,000,000 corresponds.

Aromatic polycarbonates are further examples of well-suited further constituents (a3). The proportion of polycarbonates (a3) in the plastic layer (A) can also be wide vary and depends on the requirements of the respective purpose. The A person skilled in the art can therefore determine the advantageous proportion in a simple manner on account of its Determine your specialist knowledge if necessary with the help of simple preliminary tests.

Preferably contains the plastic layer (A) or the mixture of substances (A) from which it is made exists, based on (A), 10 to 80 wt .-%, preferably 15 to 75 wt .-%, particularly preferably 20 to 70% by weight and in particular 25 to 65% by weight of at least one Polycarbonate (a3).

Examples of suitable polycarbonates (a3) are those based on diphenols of the general formula I,

wherein X represents a single bond, an alkylene group with 1 to 3 carbon atoms, an alkylidene group with 2 or 3 carbon atoms, a cycloalkylidene group, -S- or -SO ₂ -.

Examples of highly suitable diphenols I are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, of which bisphenol A and 1,1-bis (4-hydroxyphenyl) cyclohexane are particularly advantageous and are therefore used with particular preference.

Other examples of highly suitable diphenols are hydroquinone or resorcinol.

Both homopolycarbonates and copolycarbonates are as polycarbonates (a3) suitable. In addition to the bisphenol A homopolymer, the copolycarbonates are preferred of bisphenol A. Furthermore, polycarbonates containing polydiorganosiloxane, such as they are described, for example, in German Patent DE-A-33 34 782, in Consider.

The polycarbonates (a3) can be branched in a known manner. This is preferred by incorporating 0.05 to 2.0 mol%, based on the sum of the used Diphenols, on compounds with at least three phenolic hydroxyl groups.

The particularly suitable polycarbonates (a3) have relative viscosities of 1.10 to 1.50, in particular 1.25 to 1.40, which has a mass average molecular weight of 10,000 to 200,000, preferably from 20,000 to 80,000.

The production of the polycarbonates (a3) has no special methodological features, but takes place through the reaction of the diphenols with phosgene after Phase boundary process or the process in homogeneous phase, the so-called Pyridine process. The molecular weight to be set in each case is known Way by an appropriate amount of usual and known chain terminators achieved.

Examples of suitable chain terminators are phenol or p-tert-butylphenol or long-chain Alkylphenols according to German patent DE-A-28 42 005 such as 4- (1,3-tetramethyl butyl) phenol, monoalkylphenols or dialkylphenols with a total of 8 to 20 Carbon atoms in the alkyl substituents according to the German patent DE-A-35 06 472 such as p-nonylphenol, 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylpheriol, 2- (3,5-dimethylheptyl) phenol or 4- (3,5-dimethylheptyl) phenol.

The polycarbonates (a3) described above are preferably halogen-free, wherein Polycarbonates (a3), which have ppm contents of saponifiable chlorine, which from the Production of the polycarbonates (a3) with phosgene using the phase interface process are inherently considered to be halogen-free.

In addition, the plastic layer (A) or the mixture of substances (A) from which it exists, based on (A), up to 50 wt .-%, preferably up to 40 wt .-% and in particular up to 30 wt .-% fibrous or particulate and optionally electrically conductive fillers and / or reinforcing materials such as glass fibers, carbon fibers, Mineral fibers, whiskers, aluminum oxide fibers, glass balls, quartz powder, mica or Wollastonite or aluminum flakes, conductivity black or nickel-coated Contain carbon fibers for EMI (electromagnetic interference) applications.

Furthermore, the plastic layer (A) or the mixture of substances (A) from which it consists can Additives such as those commonly used in the plastics described above are contained in effective amounts.

Examples of suitable additives are dyes, pigments, antistatic agents, antioxidants, Lubricants and lubricants, mold release agents, flame retardants or stabilizers for Improvement of thermal stability, light stability, resistance to hydrolysis or Chemical resistance.

The plastic layer (A) to be used according to the invention is not produced methodological peculiarities, but takes place by producing the invention mixture of substances (A) to be used in the usual unknown manner, for example by Mixing the ingredients described above in solution or in bulk in one Kneader or an extruder, after which - if necessary after removing the Solvent - the resulting mixture of substances (A) shaping process, as shown on the  Field of thermoplastic materials are common and known, especially extrusion combined with calendering, injection molding, film blowing and / or laminating.

The further essential component of the inventive plastic molded part is at least one paint (B) on the plastic layer (A).

The coating (B) to be used according to the invention can be produced from a coating which, in the cured state, has a storage module E 'in the rubber-elastic range of at least 10 ^7.6 Pa, in particular at least 10 ^8.0 Pa, and a loss factor tan δ at 20 ° C. of a maximum of 0.1, in particular a maximum of 0.06, the storage module E 'and the loss factor tan δ being measured using dynamic mechanical thermal analysis (DMTA) on free homogeneous films with a layer thickness of 40 ± 10 μm.

The loss factor tan δ is defined as the quotient from the loss module E "and the memory module E '.

Dynamic mechanical thermal analysis is a well-known measurement method to determine the viscoelastic properties of coatings and described for example in Murayama, T., Dynamic Mechanical Analysis of Polymeric Material, Esevier, New York, 1978 and Loren W. Hill, Journal of Coatings Technology, Vol. 64, No. 808, May 1992, pages 31 to 33.

The measurements can be carried out, for example, using the MK II, MK III devices or MK IV from Rheometrics Scientific.

The storage module E 'and the loss factor tan δ are on homogeneous free films measured. The free films are produced in a known manner in that the Coating agent is applied and cured on substrates on which the Coating agent is not liable. Examples of suitable substrates are glass and Teflon and especially called polypropylene. Polypropylene has the advantage of a good one Availability and is therefore usually used as a carrier material.  

The layer thickness of the free films used for the measurement is generally 40 ± 10 µm.

The special selection of varnishes over the Wen of the memory module in the rubber-elastic The range and the dissipation factor at 20 ° C of the hardened lacquer enables in simple way of providing paint finishes (B) with the desired Property profile of good scratch resistance with good polishability, Resistance to chemicals and moisture as well as weather resistance, since both parameters can be determined by simple DMTA measurements. Furthermore, the resulting Paint finishes (B) have a high gloss and acid and base resistance is comparable to the corresponding values of conventional, thermally hardened Paints.

It is surprising that even paints that are only a medium or even a small plastic part, but a high to very high one Have memory module in the rubber-elastic area, paint (B) with a high Scratch resistance result.

In addition, the paints (B), which consist of the according to the above Criteria selected paints were produced, an excellent Adhesion to the plastic layer (A) of the plastic molding according to the invention. Coating agents with the corresponding above. are viscoelastic properties preferably by means of actinic radiation, in particular electromagnetic radiation such as near infrared light (NIR), visible light, UV radiation or X-rays and / or corpuscular radiation such as electron radiation curable lacquers. Here are the Lacquers curable with UV radiation are of advantage and are special according to the invention preferably used. In addition, varnishes based on organically modified ones Ceramic materials that are sold, for example, under the ORMOCER® brand suitable for the production of the paintwork (B).

These radiation-curable lacquers usually contain at least one, preferably several radiation-curable binders, in particular based on olefinically unsaturated prepolymers and / or olefinically unsaturated oligomers, optionally one or more reaks tivverdünner, optionally one or more photoinitiators and optionally usual paint additives.

Radiation-curable lacquers are preferably used whose viscosity at 23 ° C is less than 100 s run-down time in the DIN 4 cup, particularly preferably less than 80 s run-down time in the DIN 4 cups.

These radiation-curable paints, for example, are used as binders (meth) acrylic functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, Silicone acrylates and the corresponding methacrylates are used. To be favoured Used binders that are free of aromatic structural units. The usage of epoxy acrylates leads to hard, scratch-resistant coatings, but in the generally show weather resistance in need of improvement. Prefers Therefore, urethane (meth) acrylates and / or polyester (meth) acrylates, in particular preferably aliphatic urethane acrylates used.

Substantially silicone-free are also preferred, particularly preferred Silicone-free binders are used because the resulting varnishes contrast silicone-containing paints have improved paintability.

The polymers or oligomers used as binders usually have number average molecular weight from 500 to 50,000, preferably from 1,000 to 5,000.

Polymers and / or oligomers which are used per Have molecule at least 2, particularly preferably 3 to 6 double bonds.

The binders used preferably also have Double bond equivalent weight from 400 to 2,000, particularly preferably from 500 to 900, on. In addition, the binders preferably have a viscosity of 250 at 23 ° C. up to 11,000 mPa.s.  

Polyester (meth) acrylates are known in principle to the person skilled in the art. you are through different methods can be produced. For example, acrylic acid and / or methacrylic acid can be used directly as an acid component in the construction of the polyester. Besides there is the possibility of hydroxyalkyl esters of (meth) acrylic acid as the alcohol component to be used directly in the construction of the polyester. The are preferred Polyester (meth) acrylates but made by acrylating polyesters. For example can first be built up hydroxyl-containing polyesters, which are then covered with acrylic or be reacted with methacrylic acid. It can also initially contain carboxyl groups Polyester are built up, which are then with a hydroxyalkyl ester of acrylic or Methacrylic acid are implemented. Unreacted (meth) acrylic acid can pass through Wash out, distill, or preferably by reacting with an equivalent amount a mono- or diepoxide compound using suitable catalysts, such as e.g. B. triphenylphosphine, are removed from the reaction mixture. Regarding others Details on the production of polyester acrylates are particularly in German and European patents DE-A-33 16 593, DE-A-38 36 370, EP-A-0 054 105, DE-B-20 03 579 or EP-B-0 002 866.

Polyether (meth) acrylates are also known in principle to the person skilled in the art. you are through different methods can be produced. For example, those containing hydroxyl groups Polyethers that are esterified with acrylic acid and / or methacrylic acid by reaction of di- and / or polyhydric alcohols with different amounts of ethylene oxide and / or propylene oxide according to well known methods (cf. e.g. Houben-Weyl, Volume XIV, 2, Macromolecular Substances II, (1963)) can be obtained. Can also be used Polymerization products of tetrahydrofuran or butylene oxide.

The polyether (meth) acrylates and the polyester (meth) acrylates are made more flexible possible, for example, by corresponding OH-functional prepolymers or Oligomers (polyether or polyester-based) with longer-chain, aliphatic Dicarboxylic acids, in particular aliphatic dicarboxylic acids with at least 6 C atoms, such as adipic acid, sebacic acid, dodecanedioic acid and / or dimer fatty acids, be implemented. This flexibilization reaction can take place before or after the addition from acrylic or methacrylic acid to the oligomers or prepolymers.  

Furthermore, epoxy (meth) acrylates are also well known to the person skilled in the art and therefore need them not to be explained in more detail. They are usually made by Accumulation of acrylic acid on epoxy resins, for example on epoxy resins based Bisphenol A or other commercially available epoxy resins.

The epoxy (meth) acrylates can be made more flexible, for example, by that corresponding epoxy-functional prepolymers or oligomers with longer-chain, aliphatic dicarboxylic acids, in particular aliphatic dicarboxylic acids with at least 6 carbon atoms, such as adipic acid, sebacic acid, dodecanedioic acid and / or dimer fatty acids are implemented. This flexibility reaction can before or after the addition of acrylic or methacrylic acid to the oligomers or Prepolymers are carried out.

Urethane (meth) acrylates are also well known to the person skilled in the art and therefore need them not to be explained in more detail. They can be obtained by implementing one Di- or polyisocyanates with a chain extender from the group of Diols / polyols and / or diamines / polyamines and / or dithiols / polythiols and / or Alkanolamines and subsequent reaction of the remaining free isocyanate groups with at least one hydroxyalkyl (meth) acrylate or hydroxyalkyl ester of other ethylenic unsaturated carboxylic acids.

The amounts of chain extender, di- or polyisocyanate and hydroxyalkyl ester are preferably chosen so that

• 1. the equivalent ratio of the NCO groups to the reactive groups of the Chain extender (hydroxyl, amino or mercaptyl groups) between 3: 1 and 1: 2, preferably 2: 1, is and
• 2. the hydroxyl groups of the hydroxyalkyl esters of the olefinically unsaturated Carboxylic acids in a stoichiometric amount with respect to the isocyanate still free Groups of the prepolymer of isocyanate and chain extender are present.

It is also possible to manufacture the polyurethane acrylates by first part the isocyanate groups of a di- or polyisocyanate with at least one Hydroxyalkyl ester is implemented and the remaining isocyanate groups then with be implemented with a chain extender. In this case, too Amounts of chain extender, isocyanate and hydroxyalkyl ester chosen so that the equivalent ratio of the NCO groups to the reactive groups of the Chain extender between 3: 1 and 1: 2, preferably 2: 1 and that Equivalent ratio of the remaining NCO groups to the hydroxyl groups of Hy hydroxyalkyl ester is 1: 1. Of course, all intermediate forms are also of these two methods possible. For example, part of the isocyanate groups can be one Diisocyanates are first reacted with a diol, then another Part of the isocyanate groups with the hydroxyalkyl ester and subsequent to it remaining isocyanate groups are reacted with a diamine.

These various manufacturing processes for polyurethane acrylates are known (cf. for example the European patent specification EP-A-0 204 161) and therefore do not require any more details Description.

The urethane (meth) acrylates can be made more flexible, for example, by the fact that corresponding isocyanate-functional prepolymers or oligomers with longer-chain, aliphatic diols and / or diamines, especially aliphatic diols and / or Diamines with at least 6 carbon atoms are implemented. This flexibility The reaction can take place before or after the addition of acrylic or methacrylic acid be carried out on the oligomers or prepolymers.

The following commercially available products may also be mentioned as examples of suitable binders:
Crodamer® UVU 300 urethane acrylate from Croda Resins Ltd., Kent, Great Britain;
aliphatic urethane triacrylate Genomer® 4302 from Rahn Chemie, Switzerland;
aliphatic urethane diacrylate Ebecryl® 284 and aliphatic urethane triacrylate Ebecryl® 294 from UCB, Arzneimittelbos, Belgium;
aliphatic urethane triacrylate Roskydal® LS 2989 and aliphatic urethane diacrylate V94-504 from Bayer AG, Germany;
aliphatic hexafunctional urethane acrylate Viaktin® VTE 6160 from Vianova, Austria; or
aliphatic urethane diacrylate Laromer® 8861 from BASF AG as well as modified test products.

The binder is preferably used in one of the paints to be used according to the invention Amount of 5 to 90 wt .-%, particularly preferably from 20 to 70 wt .-%, each based on the total weight of the lacquer in the case of clear lacquers or on the weight of the lacquer without pigments and fillers in the case of pigmented systems.

The lacquers may also contain one or more reactive thinners. The Reactive diluents can be olefinically unsaturated compounds. The Reactive diluents can be mono-, di- or poly-unsaturated. They usually serve to influence the viscosity and the paint properties, such as the crosslink density.

The reactive diluent (s) are preferably used in the paints in an amount of 0 to 70 wt .-%, particularly preferably from 15 to 65 wt .-%, each based on the Total weight of the lacquer in the case of clear lacquers or on the weight of the lacquer without Pigments and fillers are used in the case of pigmented systems.

Examples of reactive diluents are (meth) acrylic acid and its esters, Maleic acid and its esters or half esters, vinyl acetate, vinyl ether, vinyl ureas and the like. Ä. used. Examples include alkylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, vinyl (meth) acrylate, Allyl (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Trimethylolpropane di (meth) acrylate, styrene, vinyl toluene, divinylbenzene, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipropylene glycol di (meth) acrylate, Hexanediol di (meth) acrylate, ethoxyethoxyethyl acrylate, N-vinylpyrrolidone, phenoxy ethyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl (meth) acrylate, butoxyethyl acrylate, Isobornyl (meth) acrylate, dimethylacrylamide and dicyclopentyl acrylate, which in the EP-A-250 631 described long-chain linear diacrylates with a Molecular weight from 400 to 4000, preferably from 600 to 2500. For example, the two acrylate groups are separated by a polyoxybutylene structure. Can be used are also 1,12-dodecyl diacrylate and the reaction product of 2 moles of acrylic acid with one mole of a dimer fatty alcohol, generally 36 carbon atoms having. Mixtures of the monomers mentioned are also suitable.

Mono- and / or diacrylates, such as, for example, are preferred as reactive diluents. B. Isobornyl acrylate, hexanediol diacrylate, tripropylene glycol diacrylate, Laromer® 8887 der BASF AG and Actilane® 423 from Akcros Chemicals Ltd., Great Britain, used. Isobornyl acrylate, hexanediol diacrylate and Tripropylene glycol diacrylate used.

The varnishes optionally contain, preferably in proportions of 0 to 10% by weight, preferably 2 to 6 wt .-%, based on the weight of the paint without pigments and Fillers, customary photoinitiators used in radiation-curable coating compositions, for example benzophenones, benzoins or benzoin ethers, preferably benzophenone. It can also, for example, those in the trade under the brands Irgacure® 184, Irgacure® 1800 and Irgacure® 500 from Ciba Geigy, Grenocure® MBF from Ralin and Products available from Lucirin® TPO from BASF AG can be used.

The paints may also contain customary paint additives, for example Light stabilizers (e.g. HALS compounds, benzotriazoles, oxalanilide, etc.), slip additives, Polymerization inhibitors, matting agents, defoamers, leveling agents and film-forming aids, e.g. B. cellulose derivatives, or others, usually in paints additives used. These paint additives are usually used in an amount of up to 50 wt .-%, preferably up to 45 wt .-%, based on the weight of the paint without Pigments and without fillers. Further examples of suitable paint additives  are described in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.

The varnishes are used in particular as clear varnishes, so that they are usually contain no or only transparent fillers and no opaque pigments. But it is it can also be used in the form of pigmented paints. In this case, the Lacquers 2 to 40 wt .-%, based on the total weight of the lacquer, one or more Pigments. Furthermore, the lacquers can still 1 to 20 wt .-%, based on the Total weight of the paint, one or more fillers included. In addition, on Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 176, "Effect pigments"; Pages 380 and 381 "Metal oxide mica pigments" to "Metal pigments"; Pages 180 and 181, "Iron Blue Pigments" to "Iron Oxide Black"; Pages 45 1 to 453, "Pigments" to "Pigment Volume Concentration"; Page 563 "Thioindigo pigments"; Page 567 "Titanium dioxide pigments"; and pages 250 ff., "Fillers"; referred.

The production of the lacquers to be used according to the invention has no methodological Special features, but takes place in the usual and known manner by mixing the components described above in solution or in the melt in suitable Mixing units such as dissolvers, stirred tanks, extruders or agitator mills, where appropriate measures are taken, for example working with lighting visible light of a wavelength of over 550 nm or with exclusion of light, around a Avoid premature crosslinking of the paints.

For further details of the manufacture and testing of the paints is on German patent DE-A-197 09 467 referenced.

To produce the coating (B) to be used according to the invention, the varnish described above preferably applied in a wet film thickness that after curing in the finished paint (B), especially clear coat (B), a Dry layer thickness of 10 to 250, preferably 15 to 200, particularly preferably 20 to 150 and in particular 20 to 100 microns results.  

The application of the paint can be done by all common application methods, such as. B. Spraying, knife coating, brushing, pouring, dipping or rolling. Preferably be Spray application methods applied, such as compressed air spraying, airless spraying, High rotation, electrostatic spray application (ESTA), optionally connected with hot spray application such as hot air hot spraying. The application can at temperatures of max. 70 to 80 ° Celsius are carried out so that suitable Application viscosities can be achieved without having a short-term effect thermal stress a change or damage to the paint and its if necessary, use overspray to be reprocessed. This is how hot spraying can be be designed so that the paint heats only very briefly in or just before the spray nozzle becomes.

The spray booth used for the application can be used, for example, with a optionally temperature-controlled circulation can be operated with a suitable Absorbent medium for the overspray, e.g. B. the paint itself is operated.

Application when illuminated with visible light of one wavelength is preferred of more than 550 nm or in the absence of light. This creates a material Modification or damage to the paint and overspray avoided.

The lacquer layer resulting on the plastic layer (A) is exposed to actinic radiation hardened.

Curing can take place after a certain period of rest. It can last for 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min. The Rest time is used, for example, for the course and for degassing the paint layers or for Evaporation of volatile components such as solvents. The rest period can be through the Use of elevated temperatures up to 90 ° C and / or due to reduced air humidity <10 g water / kg air, in particular <5 g / kg air, are supported and / or shortened, if no damage or changes to the paint layers occur, for example evaporation of the reactive diluents or premature complete crosslinking.

For curing with actinic radiation, the usual and known Radiation sources and optical auxiliary measures applied. Examples of suitable ones Radiation sources are high or low pressure mercury vapor lamps, which are optionally doped with lead to open a radiation window up to 405 nm, or Electron beam sources. Their arrangement is known in principle and can Conditions of the molded plastic part according to the invention and the process parameters be adjusted. For intricately shaped plastic molded parts such as parts from Automobile bodies can be the areas not accessible to direct radiation (Shadow areas) such as cavities, folds and other design-related Undercuts with spot, small area or all-round emitters combined with one automatic moving device for the irradiation of cavities or edges be (partially) cured.

Curing with actinic radiation under an inert gas atmosphere is preferred carried out.

The facilities and conditions of these hardening methods are described in R. Holmes, U. V. and E. B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984.

The process according to the invention described in the procedure described above Plastic moldings according to the invention can a due to their particular advantages Variety of applications can be supplied. The production of Motor vehicle bodies and commodities, including housings for electrotechnical and electronic components and furniture. In all The molded plastic parts according to the invention have a better application optical impression and a longer service life than conventional lacquered Plastic molded parts, which makes them economically particularly attractive for the user.

Examples and comparative tests Production Example 1 The production of a lacquer to be used according to the invention

A UV-curable lacquer was used for the following examples and comparative experiments from, based on the total amount of lacquer, 54% by weight of a urethane acrylate, prepared by reacting the isocyanurate of hexamethylene diisocyanate with 2-hydroxyethyl acrylate, 43% by weight 1,6-hexanediol diacrylate and 3% by weight of the photoinitiator Irgacure® 500 from Ciba Specialty Chemicals by intensive stirring using a Dissolver made.

The viscoelastic characteristics of homogeneously hardened films of the lacquer (irradiated dose: 1,500 mJ / cm ² ) were determined by DMTA measurements, as described in the German patent DE-C-197 09 467. The storage module E 'was 10 ^8.3 Pa, the loss factor tan δ at 20 ° C was 0.005.

Examples 1 and 2 and comparative experiments V1 to V4 The production of molded plastic parts according to the invention (Examples 1 and 2) and not Molded parts according to the invention (comparative tests V1 to V3) and their mechanical properties

For example 1 and comparative experiment V1, a commercially available blend was made from based on the blend, 40% by weight of ABS, which, based on ABS, 42% by weight of one Contained polybutadiene rubber, and 60 wt .-% polycarbonate (PC) used (Bayblend® T65MN from Bayer AG).

For example 2 and comparative experiment V2, a commercially available blend was based on the blend, 40 wt .-% ASA, the, based on ASA, 25 wt .-% one Contained acrylate rubber, and 60 wt .-% PC (Luran® S KR 2864C from BASF Corporation).

A commercial ASA was used for Example 3 (Luran® S 778T from the company BASF Aktiengesellschaft).  

A commercial ABS (Terluran® GP-22 from the company) was used for Example 4 BASF Aktiengesellschaft).

For Examples 1 to 4, plastic moldings according to the invention were produced which had the customary and known standardized dimensions which were required for the measurements given in Table 1, and which were coated on one side with a 50 .mu.m thick coating, made from the lacquer according to Production Example 1 were coated by UV radiation with a dose of 1,500 mJ / cm ² .

Examples 1 and 2 were used for comparative experiments V1 and V2 and for Comparative experiments V5 and V6, Examples 3 and 4 were repeated, only that the Plastic moldings were not coated with the paint.

Table 1 shows the results of the measurements according to the examples Results of the measurements according to the comparative experiments V1 in pairs (1 / V1, 21V2, 3 / V5 and 4 / V6) juxtaposed. The comparison shows that the mechanical Properties of the blends due to the coating, if at all, only very slightly in Were affected (1 / V1 and 2 / V2). The mechanical properties of ASA and ABS became relatively stronger in their level due to the painting lowered, but this was still within an acceptable range.

Example 1 was repeated for comparative experiment V3, except that instead of the blend made of ABS and PC a commercially available blend of polybutylene terephthalate (PBT) and PC has been used.

For comparative experiment V4, comparative experiment V 1 was repeated, only that instead of the blend of ABS and PC, a commercially available blend of PBT and PC has been used.

Table 1 shows the results of the measurements according to comparative tests V3 and V4 juxtaposed. The results show that the blend of PBT and PC damaged by the paint in its mechanical properties with more severe has been.

Table 1

Notched impact strength according to ISO 179-2 / 1eA, impact strength according to ISO 179-2 / 1fU (paint on the tension side) and tensile test according to ISO 527 (removal speed 5 mm / min) of plastic molded parts according to the invention (examples 1 to 4) and plastic molded parts not according to the invention (comparative tests V1 up to V6)

Example 5 The production of molded plastic parts according to the invention on the basis of an ASA / PC Blends (Luran® S KR 2864C)

For example 5, plastic molded parts according to the invention were produced from Luran® S KR 2864C, which had the customary and known standardized dimensions which were required for the tests described below, and which had a 50 μm thick coating on one side, produced from the lacquer according to the Production example 1 were coated by UV radiation with a dose of 1,500 mJ / cm ² .

The following tests were carried out with the plastic moldings according to the invention:

1. Notched impact strength according to ISO '179-2 / leA (samples along the flow direction taken)

Thickness (mm): 3.04
Toughness a _T

(kJ / m ²

): 23 ° C: 40.5; -20 ° C: 12.4.

2. Impact resistance according to ISO 179-2 / 1fU (paint on the tensile side, samples lengthways to Direction of flow taken during injection molding)

Thickness (mm): 3.04
Toughness a _T

(kJ / m ²

): 23 ° C: 60.9; -20 ° C: 68.3; -30 ° C: 54.4.

3rd puncture test according to DIN 53443 (paint side)

Thickness (mm): 3.10
W _T

(Nm): 23 ° C: 58.5; -10 ° C: 22.9
s _T

(Nm): 23 ° C: 22.7.

4. Cross cut test according to DIN 53151

Characteristic value: GT0.

The following tests were carried out according to the Daimler-Chrysler laboratory regulations or Daimler-Benz laboratory regulations (DBL) carried out. These laboratory regulations are for the professional world well known.

5. Rockfall DBL 5416

Characteristic value: 0.5.

6. Steam jet test DBL 5416

no release.

7. Constant climate change test DBL 5416/168 h, 668 h

Test duration: 168;
Degree of blistering 1 h after exercise: quantity 0, size 0
Degree of blisters 24 h after exercise: quantity 0, size 0
Test duration: 668;
Degree of blistering 1 h after exercise: quantity 0, size 0
Degree of blisters 24 h after exercise: quantity 0, size 0.

8. Chemical test DBL 5416 Assessment after storage for 24 hours at room temperature (RT)

10% sulfuric acid (1 h / RT): Characteristic value 0 Isopropanol (10 h / RT): Characteristic value 0 1% sodium hydroxide solution (1 h / RT): Characteristic value 1 1% sodium hydroxide solution (16 h / RT): Characteristic value 2 Oil soot (1 h / 70 ° C): Characteristic value 0 Tar solution (24 h / RT): Characteristic value 0 Glysantin® / water (1 h / RT): Characteristic value 0 Wesynth® 94 (10 h / RT): Characteristic value 0 Diesel (1 h / RT): Characteristic value 0 Brake fluid (1 h / RT): Characteristic value 0 Outer skin preservation (24 h / RT): Characteristic value 0

9. MIB scratch test, cross cut and cross cut after constant climate change test

The test results presented in sections 1 to 9 show that the Moldings according to the invention have very good mechanical and paint properties exhibit. The excellent adhesion of the paint on the blend should be emphasized.

Claims (19)

1. Lacquered plastic molding, containing

• A) at least one plastic layer, the
  • 1. at least one graft copolymer
  • 2. at least one rubber-elastic polymer with a glass transition temperature of below 10 ° C as a graft base
  • 3. at least one graft pad made of at least one copolymer with a glass transition temperature above 30 ° C
  contains or consists of;
  and
• B) at least one lacquer located on the plastic layer (A), producible from a lacquer which, in the hardened state, has a storage module E 'in the rubber-elastic range of at least 10 ^7.6 Pa and a loss factor tan δ at 20 ° C of a maximum of 0.1, whereby the storage module E 'and the loss factor tan δ were measured with dynamic mechanical thermal analysis (DMTA) on free homogeneous films with a layer thickness of 40 ± 10 µm.

2. The plastic molding according to claim 1, characterized in that the lacquer in the cured state has a storage module E in the rubber-elastic range of at least 10 ^8.0 Pa and a loss factor tan δ at 20 ° C of a maximum of 0.06. 3. The plastic molding according to claim 1 or 2, characterized in that the Lacquer is curable with actinic radiation. 4. The plastic molding according to claim 3, characterized in that the paint with electromagnetic radiation and / or corpuscular radiation is curable. 5. The plastic molding according to one of claims 1 to 4, characterized in that the rubber-elastic polymer (a11) natural rubber, a synthetic rubber based on conjugated dienes and / or an elastomer based on C ₁ - to C ₈ alkyl esters Is acrylic acid. 6. The plastic molding according to one of claims 1 to 5, characterized in that the copolymer (a12)

• 1. at least one vinyl aromatic monomer and / or at least one alkyl (meth) acrylate and
• 2. acrylonitrile, methacrylonitrile, maleic anhydride and / or at least one maleimide with C ₁ - to C ₈ -alkyl or C ₆ - to C ₂₀ -aryl groups

polymerized contains. 7. The plastic molding according to one of claims 1 to 6, characterized in that the graft copolymer (a1) is a Acrylonitrile-butadiene-styrene graft copolymer (ABS) or around one Acrylonitrile-styrene-acrylate graft copolymer (ASA). 8. The plastic molding according to one of claims 1 to 7, characterized in that the plastic layer (A) still

• 1. at least one ungrafted copolymer which contains at least one monomer (a121) and at least one monomer (a122) in copolymerized form,

contains. 9. The plastic molding according to one of claims 1 to 8, characterized in that the plastic layer (A) still

• 1. at least one polycarbonate

contains. 10. A method for producing a painted plastic molding containing

• A) at least one plastic layer, the
  • 1. at least one graft copolymer
  • 2. at least one rubber-elastic polymer with a glass transition temperature of below 10 ° C as the graft base
  • 3. at least one graft pad made of at least one copolymer with a glass transition temperature above 30 ° C
  contains or consists of;
  and
• B) at least one paint job

by applying at least one lacquer to the surface of the plastic layer (A) and hardening the resulting lacquer layer, which results in the lacquer (B), characterized in that a lacquer is used which, in the hardened state, has a storage module E 'in the rubber-elastic range of at least 10 ^7.6 Pa and a loss factor tan δ at 20 ° C of a maximum of 0.1, the memory module E 'and the loss factor tan δ with the dynamic mechanical thermal analysis (DMTA) on free homogeneous films with a layer thickness of 40 ± 10 µm were measured. 11. The method according to claim 10, characterized in that the lacquer in the cured state has a storage module E 'in the rubber-elastic range of at least 10 ^8.0 Pa and a loss factor tan δ at 20 ° C of a maximum of 0.06. 12. The method according to claim 10 or 1 l, characterized in that the paint is curable with actinic radiation. 13. The method according to claim 12, characterized in that the paint with electromagnetic radiation and / or corpuscular radiation is curable. 14. The method according to any one of claims 10 to 13, characterized in that the rubber-elastic polymer (a11) natural rubber, a synthetic rubber based on conjugated dienes and / or an elastomer based on C ₁ - to C ₈ alkyl esters of Is acrylic acid. 15. The method according to any one of claims 10 to 14, characterized in that the copolymer (a12)

• 1. at least one vinyl aromatic monomer and / or at least one alkyl (meth) acrylate and
• 2. acrylonitrile, methacrylonitrile, maleic anhydride and / or at least one maleimide with C ₁ - to C ₈ -alkyl or C ₆ - to C ₂₀ -aryl groups

polymerized contains. 16. The method according to any one of claims 10 to 15, characterized in that it is the graft copolymer (a1) Acrylonitrile-butadiene-styrene graft copolymer (ABS) or around Acrylonitrile-styrene-acrylate graft copolymer (ASA). 17. The method according to any one of claims 10 to 16, characterized in that the plastic layer (A) still

• 1. at least one ungrafted copolymer which contains at least one monomer (a121) and at least one monomer (a122) in copolymerized form,

contains. 18. The method according to any one of claims 10 to 17, characterized in that the plastic layer (A) still

• 1. at least one polycarbonate

contains. 19. Use of the molded plastic parts according to one of claims 1 to 9 and / or of those produced by the method according to one of claims 10 to 18 Plastic moldings for the production of motor vehicle bodies and Commodities, including housings for electrotechnical and electronic Components and furniture.