DE102005049520A1 - Production of moulded parts, e.g. bumpers or tailgates for cars, involves in-mould plastic injection onto a preformed carrier film coated with a pigmented basecoat and a special, urethane-acrylate based clearcoat - Google Patents

Abstract

Moulded parts, especially for cars, are made by an in-mould injection process using a carrier film coated with a pigmented basecoat and a crosslinkable clearcoat based on urethane-(meth)acrylate material with branching points, cyclic units and aliphatic units, which also contains carbamate, biuret, allophanate, urea and/or amide groups : A method for the production of moulded parts, especially for cars, involves (I) making a film (F) with a coating (B) by (1) applying a pigmented coating material (P) to an optionally pretreated surface (T1) of a carrier film (T), (2) applying a crosslinkable coating material (K) which contains a radically-crosslinkable component (KK) and gives a transparent coating (KE) after final crosslinking, and (3) drying and/or partly crosslinking material (K) to give a coating which is not finally crosslinked (KT), (II) placing the film (F) in an open mould, (III) closing the mould, contacting the other side (T2) of the carrier (T) with a fluid or softened plastic material (KM) and allowing the material (KM) to set, (IV) demoulding the part and (V) finally crosslinking the coating (KT). The crosslinkable component (KK) contains oligo- and/or poly-urethane (meth)acrylate(s), shows on average more than 1 ethylenic double bonds per molecule, a number-average mol. wt. (M n) of 1000-10000, a double bond content of 1.0-5.0 mols/1000 g KK and on average more than one branching point per molecule, contains 5-50 wt% cyclic structural units and contains at least one aliphatic structural unit with at least 6 carbons in the chain. Component (KK) also contains carbamate and/or biuret and/or allophanate and/or urea and/or amide groups (C/B/A/U/A groups), and (P) is a solvent-containing or aqueous coating material. Independent claims are also included for (1) film (F) with a coating (B), obtained by the above method (2) moulded parts consisting of material (KM) coated with film (F) .

Description

Territory of invention

• I. eine eine Beschichtung (B) aufweisende Folie (F) herstellt, indem auf eine ggf. vorbehandelte Oberfläche (T1) einer thermoplastischen Trägerfolie (T) 1. ein pigmentiertes Beschichtungsmittel (P) aufgebracht wird, 2. ein vernetzbares Beschichungsmittel (K), das eine radikalisch vernetzbare Komponente (KK) enthält und das nach der Endvernetzung eine transparente Beschichtung (KE) ergibt, aufgebracht wird, 3. das in Stufe 2 aufgebrachte Beschichtungsmittel (K) getrocknet und/oder partiell vernetzt wird, wodurch eine noch nicht endvernetzte Beschichtung (KT) erzeugt wird,
• II. die in Stufe I. hergestellte Folie (F) in ein geöffnetes Werkzeug einlegt,
• III. das Werkzeug geschlossen, die der Oberfläche (T1) abgewandte Seite (T2) der thermoplastischen Trägerfolie (T) mit einem flüssigen oder erweichten Kunststoffmaterial (KM) in Berührung gebracht wird und sich das Kunststoffmaterial verfestigen lassen wird,
• IV. das in Stufe III. erhaltene Formteil dem Werkzeug entnommen wird und
• V. die Beschichtung (KT) zu einem beliebigen Zeitpunkt im Verlaufe des Verfahrens endvernetzt wird,

wobei das vernetzbare Beschichtungsmittel (K) eine radikalisch vernetzbare Komponente (KK) enthält, die

• (i) ein oder mehrere Oligo- und/oder ein oder mehrere Polyurethan(meth)acrylate enthält und
• (ii) im Mittel mehr als 1, vorzugsweise mindestens 2 und insbesondere mehr als 2 bis 10,0, ethylenisch ungesättigte Doppelbindungen pro Molekül,
• (iii) ein zahlenmittleres Molekulargewicht von 1.000 bis 10.000 g/mol, bevorzugt von 2.000 bis 5.000 g/mol und besonders bevorzugt von 2.500 bis 3.500 g/mol,
• (iv) einen Doppelbindungsgehalt von 1,0 bis 5,0 mol Doppelbindungen pro 1.000 g reaktive Komponente (KK), vorzugsweise einen Doppelbindungsgehalt von 1,5 bis 4,0 mol Doppelbindungen pro 1.000 g reaktive Komponente (KK) und besonders bevorzugt von mehr als 2,0 bis 3,5 mol Doppelbindungen pro 1.000 g reaktive Komponente (KK),
• (v) im Mittel pro Molekül > 1, bevorzugt > 1,4, besonders bevorzugt >2 Verzweigungspunkte,
• (vi) 5-50 Gew.-%, vorzugsweise 10 – 40 Gew.-%, besonders bevorzugt 15 – 30 Gew.-%, jeweils bezogen auf das Gewicht der Komponente (KK), cyclische Strukturelemente und
• (vii) mindestens ein aliphatisches Strukturelement mit mindestens 6 C-Atomen in der Kette

aufweist.The present invention relates to a process for the production of molded parts, in particular for use in the automotive industry, in which

• I. produces a film (F) having a coating (B) by applying to a possibly pretreated surface (T1) of a thermoplastic carrier film (T) 1. a pigmented coating agent (P), 2. a crosslinkable coating agent (K) which comprises a radically crosslinkable component (KK) and which after the final crosslinking gives a transparent coating (KE) is applied, 3. the coating agent (K) applied in step 2 is dried and / or partially crosslinked, whereby a not yet finally crosslinked Coating (KT) is generated,
• II. Inserting the film (F) prepared in step I into an opened mold,
• III. the tool is closed, the side (T2) of the thermoplastic carrier film (T) facing away from the surface (T1) is brought into contact with a liquid or softened plastic material (KM) and the plastic material is solidified,
• IV. That in stage III. obtained molding is removed from the tool and
• V. the coating (KT) is cross-linked at any time in the course of the process,

wherein the crosslinkable coating agent (K) contains a radically crosslinkable component (KK) which

• (i) one or more oligo- and / or one or more polyurethane (meth) acrylates containing and
• (ii) an average of more than 1, preferably at least 2 and in particular more than 2 to 10.0, ethylenically unsaturated double bonds per molecule,
• (iii) a number-average molecular weight of from 1,000 to 10,000 g / mol, preferably from 2,000 to 5,000 g / mol and more preferably from 2,500 to 3,500 g / mol,
• (iv) a double bond content of 1.0 to 5.0 moles of double bonds per 1,000 g of reactive component (KK), preferably a double bond content of 1.5 to 4.0 moles of double bonds per 1,000 g of reactive component (KK), and more preferably more as 2.0 to 3.5 moles of double bonds per 1,000 g of reactive component (KK),
• (v) on average per molecule> 1, preferably> 1.4, more preferably> 2 branch points,
• (vi) 5-50 wt .-%, preferably 10 - 40 wt .-%, particularly preferably 15 - 30 wt .-%, each based on the weight of component (KK), cyclic structural elements and
• (vii) at least one aliphatic structural element having at least 6 C atoms in the chain

having.

The The present invention also relates to the use of the like available Moldings and for that Process suitable films having a coating (F).

moldings from a provided with a foil plastic material are the Specialist known. Instead of plastic components with a foil too To conceal or glue, one goes now also in industrial one Applications reinforced about, the foils directly in the forming tool with the plastic material to inject, press behind or foam behind (A. Grefenstein, "Folienhinterspritzen instead of painting, new technology for Plastic body parts "in metal surface, 10/99, 53rd year, Carl Hanser Verlag, Munich, 1999).

The for the production of moldings used multilayer, color and / or effect films include, as is known a carrier foil, at least a color and / or effect basecoat and a clearcoat. They correspond in their structure to the conventional color and / or effect Coating systems.

Especially in the field of automotive painting, however, a large number of requirements are placed on the appearance of the film-side surfaces of the molded parts (cf., for example, the European Patent EP 0 352 298 B1 , Page 15, line 42 to page 17, line 40).

With The solutions proposed in the prior art can these customary in the field of automotive painting Requirements are met but insufficient. Besides, they are the solutions proposed in the prior art partly with regard to on the for the value to be set for the radiation-crosslinkable clearcoat materials used the glass transition temperature even contradictory.

Thus, from WO 00/63015 a method of the type mentioned for the production of moldings is known in which the crosslinkable coating composition (K) consists of a radiation-crosslinkable composition containing a binder having a glass transition temperature above 40 ° C. However, the end-crosslinked transparent coatings (KE) obtained in this process have unsatisfactory properties. In particular, a insufficient crosslinking of the transparent coating (KE) obtained.

Furthermore are used in the process described in WO 00/63015 as a pigmented coating agent thermoplastic polymers, the dyes or pigments in the polymer layer distributed, used. This color is applied Layer by extrusion while the use of solvent-containing or aqueous, pigmented Coating agents and their application methods are not described are.

Farther is from EP-A-819 516 a method for the production of moldings in which a provided with a coating film in a Mold inserted, the mold closed and with a Plastic material (KM) in contact brought and the plastic material (KM) is solidified, wherein the method is characterized in that the coating material before the introduction of the plastic material only partially cross-linked and only during and / or crosslinked after the introduction of the plastic material (KM) becomes. Radiation-crosslinkable coating compositions are preferred in the process with a glass transition temperature below 40 ° C, especially based on urethanes used. Details on However, the composition of suitable coating agents are not contain. Further, from EP-B-403 573 one with a coating provided foil for the use described in the thermoforming process, wherein it is essential that an uncrosslinked or less networked Clearcoat with a glass transition temperature below 20 ° C forms at least part of the clearcoat film.

Finally are from EP-B-1 144 476 both by thermal addition and by radiation-induced addition curable, so-called dual cure, Coating compositions and their use for the production of thermoformable paint films known. However, the coating compositions described therein contain for the thermal curing required free isocyanate groups. The coating agents have So a materially complex Composition on.

Besides that is the process control difficult to uncontrolled curing of the thermally reactive Ingredients during the thermal process steps, such as. thermoforming at elevated temperature, to avoid.

Of the The present invention was therefore based on the object, a method to provide for the production of moldings, on the one hand Ensures adequate crosslinking of the coating agent (K) is. On the other hand, however, the not yet finally cross-linked coating (KT) may no longer flow and not be embossed by a possibly applied protective film.

So especially when using the moldings in the automotive industry the moldings in their film-side appearance the requirements satisfy a so-called Class A surface.

In addition, the molded parts in their film-side appearance should meet the requirements usually imposed on an automotive finish (see European Patent EP 0 352 298 B1 , Page 15, line 42 to page 17, line 40). In particular, both the weathering resistance and the chemical resistance of the finally cross-linked transparent coating (KE) must not be worse than the conventional automotive clearcoat films. Finally, the end-crosslinked coating (KE) should also have sufficient scratch resistance.

Solution of task

• 1. die radikalisch vernetzbare Komponente (KK) Carbamat- und/oder Biuret- und/oder Allophanat- und/oder Harnstoff- und/oder Amidgruppen enthält und
• 2. als pigmentiertes Beschichtungsmittel (P) ein lösemittelhaltiges oder ein wässriges Beschichtungsmittel eingesetzt wird.

This object is surprisingly achieved by a method of the type mentioned, which is characterized in that

• 1. the radically crosslinkable component (KK) contains carbamate and / or biuret and / or allophanate and / or urea and / or amide groups, and
• 2. As pigmented coating agent (P) a solvent-containing or an aqueous coating agent is used.

object The present invention also includes those in the process used, a coating (B) having films (F) and the provided with the film (F) moldings and their use.

Advantages of invention

It is surprising and was unpredictable that by using the special Component (KK) in the crosslinkable coating compositions (K) coatings are obtained, on the one hand not yet cross-linked Coating (KT) no longer flows and by a possibly applied Protective film not embossed and on the other hand in the final curing sufficient cross-linking the coating agent (K) is given.

The method according to the invention thus provides moldings which, in their film-side appearance, ensure Class A surfaces and which fulfill the requirements usually imposed on an automobile finish len (see European Patent EP 0 352 298 B1 , Page 15, line 42 to page 17, line 40). In particular, both the weathering resistance and the chemical resistance of the finally crosslinked transparent coating (KE) are no worse than the conventional automotive clearcoat films. Finally, the end-crosslinked coating (KE) also has sufficient scratch resistance.

Full Description of the invention

The at the inventive method used materials

The one coating (B) having film (F)

Crosslinkable coating agent (K)

It is essential to the invention that in the crosslinkable coating composition (K) radically crosslinkable component (KK) a or a plurality of oligourethane (meth) acrylates and / or one or more polyurethane (meth) acrylates contains.

Here and hereinafter, an oligomer is a compound which generally has on average 2 to 10 basic structures or Having monomer units. Under a polymer, however, is a Compound understood, which in general more than 10 basic structures or monomer units. Mixtures or Material entities of this kind are also used by experts referred to as binders or resins.

in the Difference here and below is under a low molecular weight Connection to understand a connection, which is essentially derives only from a basic structure or a monomer unit.

Prefers contains the radically crosslinkable component (KK) at least 50% by weight, more preferably at least 70% by weight, and most preferably at least 80 wt .-%, each based on the solids content component (KK), one or more oligourethane (meth) acrylates and / or one or more polyurethane (meth) acrylates. Especially is the radically crosslinkable component to 100% of one or a plurality of oligourethane (meth) acrylates and / or one or more Polyurethane (meth) acrylates.

Prefers contains the radically crosslinkable component (KK) also at most 50 wt .-%, especially preferably at most 30% by weight and most preferably not more than 20 and in particular no further radically crosslinkable components.

Prefers contains while the radically crosslinkable component (KK) less than 5 Wt .-%, preferably less than 1 wt .-%, each based on the Weight of the component (KK), and in particular substantially none detectable, free isocyanate groups.

Besides that is it is preferred that the in the crosslinkable coating agent (K) contained radically crosslinkable component (KK) a mixture of different Oligo- and / or polyurethane (meth) acrylates, which are also different Double bond contents, molecular weights, double bond equivalent weights, Content of branching points and contents of cyclic and long-chain aliphatic structural elements and different content Carbamate, biuret, allophanate, amide and / or urea groups can have contains.

These Mixture can be obtained in that different Oligo- or polyurethane (meth) acrylates are mixed, or that at the preparation of a corresponding oligo- or polyurethane (meth) acrylate at the same time different products are created.

Next The urethane (meth) acrylates come as further radically crosslinkable Components of the component (KK) monomers, but preferably oligomers and / or polymers, in particular polyester (meth) acrylates, epoxy (meth) acrylates, (meth) acrylic-functional (meth) acrylic copolymers, polyether (meth) acrylates, unsaturated Polyesters, amino (meth) acrylates, melamine (meth) acrylates and / or silicone (meth) acrylates, preferably polyester (meth) acrylates and / or epoxy (meth) acrylates and / or Polyether (meth) acrylates, into consideration. Preference is given to polymers, the additional to the double bonds still hydroxyl, carboxyl, amino and / or Contain thiol groups.

to Achieving good crosslinking is preferably radically crosslinkable Components (KK) with a high reactivity of the functional groups used, more preferably radically crosslinkable components (KK), which contain acrylic double bonds as functional groups.

The Urethane (meth) acrylates can in a manner known to those skilled in the art from isocyanate group-containing compound and at least one compound containing isocyanate-reactive groups contains by mixing the components in any order, optionally at elevated temperature, getting produced.

Preference is given to the compound containing isocyanate-reactive groups, added to the isocyanate group-containing compound, preferably in several steps.

Especially For example, the urethane (meth) acrylates are obtained by the di- or polyisocyanate and then at least one hydroxyalkyl (meth) acrylate or hydroxyalkyl esters of other ethylenically unsaturated carboxylic acids will, by what, first a part of the isocyanate groups is reacted. The following is a chain extender from the group of diols / polyols and / or diamines / polyamines and / or dithiols / polythiols and / or alkanolamines and so the remaining isocyanate groups reacted with the chain extender.

Besides that is it is possible to prepare the urethane (meth) acrylates by reacting a di- or polyisocyanates with a chain extender and subsequent reaction the remaining free isocyanate groups with at least one ethylenic unsaturated Hydroxyalkyl.

Of course they are also all Intermediate forms of these two methods possible. For example, can a portion of the isocyanate groups of a diisocyanate with a diol can be implemented, then another part the isocyanate groups with the ethylenically unsaturated hydroxyalkyl ester and following this can they remaining isocyanate groups are reacted with a diamine.

In As a rule, the reaction at temperatures between 5 and 100 ° C, preferred between 20 to 90 ° C and more preferably between 40 and 80 ° C and especially between 60 and 80 ° C performed.

Prefers is worked under anhydrous conditions. anhydrous means that the Water content in the reaction system is not more than 5 wt .-%, preferably not more than 3% by weight, and more preferably not more than 1% by weight.

Around to suppress a polymerization of the polymerizable double bonds, is preferably worked under an oxygen-containing gas, especially preferably air or air-nitrogen mixtures.

When oxygen-containing gas can preferably air or a mixture of oxygen or air and a be used under the inert gas conditions. As inert Gas can Nitrogen, helium, argon, carbon monoxide, carbon dioxide, water vapor, lower hydrocarbons or mixtures thereof are used.

Of the Oxygen content of the oxygen-containing gas, for example between 0.1 and 22% by volume, preferably from 0.5 to 20, especially preferably 1 to 15, very particularly preferably 2 to 10 and in particular 4 to 10% by volume. Of course can, if desired, also higher Oxygen levels are used.

The Reaction can also be carried out in the presence of an inert solvent e.g. Acetone, isobutyl methyl ketone, methyl ethyl ketone, toluene, xylene, Butyl acetate or ethoxyethyl acetate.

By Selection of the type and amount of di- and / or polyisocyanate used, Chain extender and hydroxyalkyl esters are the other characteristics of the Urethane (meth) acrylates, such as. B. double bond content, double bond equivalent weight, Content of branching points, content of cyclic structural elements, Content of aliphatic structural elements with at least 6 C atoms, on biuret, allophanate, carbamate, urea or amide groups u. Ä. Controlled.

By the selection of the amounts of di- or polyisocyanate used in each case and chain extenders as well as through the functionality of the chain extender it is also possible, urethane (meth) acrylates to produce, in addition to the ethylenically unsaturated double bonds still other functional groups, for example hydroxyl, carboxyl groups, Amino groups and / or thiol groups or the like contain. Preferably included while the urethane (meth) acrylates still hydroxyl and / or carboxyl groups.

Especially, when the urethane (meth) acrylates in aqueous coating compositions (K) are used, part of the in the reaction mixtures existing free isocyanate groups still reacted with compounds, the one isocyanate-reactive group, preferably selected from the group consisting of hydroxyl, thiol and primary and secondary Amino groups, in particular hydroxyl groups, and at least one, especially one, acid group, preferably selected from the group consisting of carboxyl groups, sulfonic acid groups, phosphoric acid groups and phosphonic acid groups, in particular carboxyl groups. Examples of suitable compounds of this type are hydroxyacetic acid, hydroxypropionic acid or Gamma-hydroxybutyric acid, especially hydroxyacetic acid.

The polyester (meth) acrylates which are suitable in addition to the urethane (meth) acrylates are known in principle to the person skilled in the art. They can be produced by various methods. For example, acrylic acid and / or methacrylic acid can be used directly as the acid component in the construction of the polyester the. In addition, it is possible to use hydroxyalkyl esters of (meth) acrylic acid as alcohol component directly in the construction of the polyester. However, the polyester (meth) acrylates are preferably prepared by acrylation of polyesters. For example, first hydroxyl-containing polyesters can be constructed, which are then reacted with acrylic or methacrylic acid. It is also possible initially to form carboxyl-containing polyesters, which are then reacted with a hydroxyalkyl ester of acrylic or methacrylic acid. Unreacted (meth) acrylic acid can be removed from the reaction mixture by washing, distilling or, preferably, by reacting with an equivalent amount of a mono- or di-epoxide compound using suitable catalysts such as triphenylphosphine. For further details on the preparation of the polyester acrylates, reference may be made in particular to DE-OS 33 16 593 and the DE-OS 38 36 370 and also to EP-A-54 105, DE-AS 20 03 579 and EP-B-2866.

Also the further suitable polyether (meth) acrylates are those skilled in the art also known in principle. They are by different methods produced. For example, you can hydroxyl-containing polyethers esterified with acrylic acid and / or methacrylic acid be, by reacting di- and / or polyhydric alcohols with various amounts of ethylene oxide and / or propylene oxide well known methods (see, e.g., Houben-Weyl, Volume XIV, 2, Macromolecular Substances II, (1963)). It is also possible to use polymerization products of tetrahydrofuran or butylene oxide.

By Selection of the type and amount of alcohol and acid component used Become the other characteristics of the Polyether (meth) acrylates and polyester (meth) acrylates, such as. B. double bond content, Double bond equivalent weight, content at branch points, content of cyclic structural elements, Content of aliphatic structural elements with at least 6 C atoms u. Ä. Controlled.

Further Epoxy (meth) acrylates are well known and need the skilled person therefore not closer explained to become. They are usually made by addition of acrylic acid to epoxy resins, for example on epoxy resins based on bisphenol A or other commercially available epoxy resins.

It is also essential to the invention that the radically crosslinkable Component (KK) on average more than 1, preferably at least 2 ethylenically unsaturated Double bonds per molecule having. Particularly preferably, the radically crosslinkable Component (KK) more than 2 to a maximum of 10.0, in particular 3.0 to 9.5, preferably 3.5 to 9.0, and most preferably 4.0 to 8.5 double bonds per molecule on.

in the General contains the radically crosslinkable component (KK) not more than 10% by weight Compounds that are only a curable Group, preferably not more than 7.5% by weight, more preferably not more than 5% by weight, most preferably not more than 2.5 Gew%, in particular not more than 1% by weight and especially 0% by weight.

With increasing double bond content per molecule of the radically crosslinkable Component (KK) generally increases the crosslink density the end-crosslinked transparent coating (KE). simultaneously However, it generally increases with double bond content per molecule of radically crosslinkable component (KK) the elongation at break of the end-crosslinked transparent coating (KE), i. the system becomes more brittle. Therefore has the end-crosslinked transparent coating (KE) with rising Double bond content per molecule an increased Tendency to stress cracks after UV curing on.

The introduction The double bonds in the component (KK) are carried out as above generally described by reaction of one or more ethylenically unsaturated Hydroxyalkylestern with the isocyanate groups of the isocyanate or of the isocyanate prepolymer in the case of urethane (meth) acrylates or with the acid groups of the polyester in the case of polyester (meth) acrylates. Likewise, like described above, the Ausgangsoligo- or starting polymers, such as e.g. Polyesters, polyethers, epoxies and acrylate polymers, with acrylic and / or methacrylic acid and / or another ethylenically unsaturated Acid reacted become.

Examples for suitable ethylenically unsaturated Hydroxyalkyl esters are hydroxyalkyl esters of acrylic and methacrylic acid, the Maleic and fumaric acid, the croton and isocrotonic acid and vinylacetic acid, preferably ethylenically unsaturated Hydroxyalkyl esters of acrylic acid. Particularly preferred are the ethylenically unsaturated hydroxyethyl and / or Hydroxypropyl and / or hydroxybutyl and / or hydroxypentyl and / or Hydroxyhexyl esters, most preferably ethylenically unsaturated hydroxyethyl esters or ethylenically unsaturated hydroxyethyl esters together with ethylenically unsaturated Hydroxybutylestern, said unsaturated acids, in particular of acrylic acid used.

Of course, hydroxyalkyl esters having more than one double bond per molecule can also be used to introduce the double bonds into the component (KK), for example pentaerythene ritdi, Pentaerythrittri- and pentaerythritol tetra-acrylate ö.ä.

All is particularly preferred for the introduction of the double bonds in the component (KK) 2-hydroxyethyl acrylate and / or 4-hydroxybutyl acrylate and / or pentaerythritol triacrylate used.

there has the introduction the double bond used depending on their structure circumstances itself influence the properties of the coating, in addition to the Double bond content under circumstances also other sizes, e.g. the urethane group content, changed become. For example, the double bond content of the component (KK) increased by the existence Part of the chain extender is replaced by hydroxyethyl acrylate, the urethane group content becomes according to the mass ratio of chain extender changed to hydroxyethyl acrylate. If, however, the double bond content of the component (KK), for example increased by that instead of of hydroxyethyl acrylate hydroxyalkyl ester having more than one double bond per molecule, like e.g. Pentaerythritol triacrylate and / or pentaerythritol tetraacrylate, used, the urethane group content is moderately lowered.

It is also essential to the invention that the radically crosslinkable Component (KK) has a number average molecular weight of 1,000 to 10,000 g / mol, preferably from 2,000 to 5,000 g / mol and especially preferably from 2,500 to 3,500 g / mol.

ever higher here the molecular weight of the reactive component (KK) is lower is generally the crosslink density of the final crosslinked transparent Coating (KE).

simultaneously is the consistency in general the not yet cross - linked transparent coating (KT) in Generally higher The higher while the molecular weight of the reactive component (KK) is.

Farther it is essential to the invention that the radically crosslinkable component (KK) has a double bond content of 1.0 to 5.0 mol double bonds per 1,000 g of reactive component (KK), preferably a double bond content from 1.5 to 4.0 moles of double bonds per 1,000 g of reactive component (KK) and more preferably a double bond content of more as 2.0 to 3.5 moles of double bonds per 1,000 g of reactive component (KK), , wherein the values are each based on the weight of radically crosslinkable component (KK), but of course without non-reactive components, such as. As solvents, water or additives.

Of the Double bond content of the component (KK) depends - as known in the art - in addition the content of double bonds per molecule, especially with the number average Molecular weight of the component (KK) together.

With decreasing double bond content of the component (KK) becomes the property improves that the dried, but not yet cross-linked transparent Coating (KT) stops flowing and possibly applied Protective film no longer embossed becomes.

simultaneously decreases with decreasing double bond content of the component (KK) in the Generally, the crosslink density of the final crosslinked transparent Coating (KE) from.

As The person skilled in the art, while the molecular weight and the Double bond content over Type and quantity of structural components used as well as the Reaction conditions are set.

Farther it is essential to the invention that the radically crosslinkable component (KK) on average per molecule> 1, preferably> 1.4, more preferably> 2 branch points having.

at a decrease in the average number of branch points per molecule in component (KK), in general, the scratch resistance of finally cross-linked transparent coating (KE). At the same time takes with decreasing the mean number of branch points per molecule in general the resistance the dried but not yet fully crosslinked transparent coating (KT).

The average number of branch points per molecule in component (KK) generally by the content of for the construction of the component (KK) used compounds having a functionality greater than 2, in particular with a functionality of at least 3, set.

The Branching points of the radically crosslinkable component (KK) are preferred over the Use of isocyanates having a functionality greater than 2, in particular with a functionality of at least 3, introduced.

The branching points are particularly preferably introduced by using trimeric and / or polymeric isocyanates, in particular isocyanurates, and / or adducts or prepolymers having an isocyanate functionality for preparing the oligo- and / or polyurethane (meth) acrylates used in the free-radically crosslinkable component (KK) greater than 2, in particular allophanates and / or biurets used become. Most preferably, the branching points are introduced via the use of one or more isocyanurates and / or one or more biurets.

It but it is also possible in the construction of the radically crosslinkable component (KK) alcohols, thiols or amines with a functionality greater than 2, for example by the use of pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, Ditrimethylolpropane and trishydroxyethyl isocyanurate.

It is also Essential to the invention that the radically crosslinkable component (KK) 5-50 wt .-%, preferably 10 - 40 wt .-%, particularly preferably 15 - 30 Wt .-%, each based on the weight of component (KK) (but Of course without non-reactive components, such as. Solvent, water or additives) having cyclic structural elements.

With increasing content of cyclic structural elements of the component (KK) i.A. the property improves that the dried, but not yet cross-linked transparent coating (KT) not more flows and is no longer embossed by a possibly applied protective film.

With increasing content of cyclic structural elements of the component (KK) takes i.A. also the chemical resistance, the weather resistance and the scratch resistance of the final crosslinked transparent coating (KE) too. Furthermore, it decreases with too high a content of cyclic structural elements the component (KK) the elongation at break the end-crosslinked coating (KE) and thus the brittleness to.

It it is preferred that the radically crosslinkable component (KK) as cyclic structural elements monocyclic structural elements with 4 to 8, particularly preferably with 5 to 6 ring members, and / or Polycyclic structural elements with 7 to 18 ring members, especially preferably di- and / or tricyclic structural elements with preferably 10 to 12, especially preferably tricyclodecane rings, and / or that the cyclic Structural elements are substituted.

The cyclic structural units can be both cycloaliphatic, heterocyclic and aromatic, wherein the structural units are preferably cycloaliphatic and / or are heterocyclic. In particular, a combination of cycloaliphatic and heterocyclic structural units used.

The heterocyclic structural units may be in the chain - such as. B. when using uretdiones - and / or the branch points make up - like z. B. when using isocyanurates. The cycloaliphatic structural units can also to be in the chain - like z. B. when using cycloaliphatic diols, such as hydrogenated Bisphenol-A, to build up the urethanes - and / or the branch points form. The heterocyclic structural units particularly preferably form but the branch points while are the cycloaliphatic structural units in the chain.

preferred cycloaliphatic structural elements are optionally substituted cyclopentane rings, optionally substituted cyclohexane rings, optionally substituted dicycloheptane rings, optionally substituted dicyclooctane rings and / or optionally substituted Dicyclodecane rings and / or optionally substituted tricyclodecane rings, in particular optionally substituted tricyclodecane rings and / or optionally substituted cyclohexane rings.

The heterocyclic structural units can be both saturated, unsaturated as also be aromatic. Preferred are saturated heterocyclic structural units used.

The Heteroatoms are preferably selected from the group nitrogen and / or oxygen and / or sulfur and / or phosphorus and / or Silicon and / or boron, more preferably nitrogen. The number the heteroatom per ring is usually 1 to 18, preferably 2 to 8, and most preferably 3.

Especially Isocyanurate rings are preferred as heterocyclic structural units and / or uretdiones and / or optionally substituted triazine rings, completely particularly preferably isocyanurate rings used.

to introduction The cyclic structural elements are in principle also aromatic Structural elements suitable, wherein preferably the content of aromatic Structural elements not more than 10% by weight, preferably not more than 5% by weight, and particularly preferably at most 2 wt .-%, each based on the Weight of the component (KK) is. Aromatic structural elements namely have generally adverse effects on weather resistance the resulting end-crosslinked transparent coating (KE), so that the content of aromatic structural elements therefore often limited is.

The introduction of the cyclic structural elements in the reactive component (KK) is carried out by using appropriate compounds with cyclic structural elements for the preparation of the component (KK). In particular, for the preparation of the component (KK) di- and / or polyisocyanates with cyclic structural elements and / or di- or Polyols, di- or polyamines, di- or polythiols can be used with cyclic structural elements. Particular preference is given to using di- and / or polyols and / or di- and / or polyisocyanates with cyclic structural elements.

to Preparation of the Radically Crosslinkable Component (CC) used oligo- and / or polyurethane (meth) acrylates are therefore preferred at least proportionally as isocyanate component isocyanurates of di- and / or polyisocyanates, usually used in the paint industry. Instead or together with these isocyanurates, prepolymers and / or adducts, in particular biurets and / or allophanates and / or uretdiones, of Di- and / or polyisocyanates, commonly used in the paint industry can be used. Particularly preferred Isocyanurates and / or biurets and / or allophanates and / or uretdiones used by aliphatic and / or cycloaliphatic isocyanates. Besides is it also possible alone or in combination with the above-listed isocyanurates and / or Biurets and / or allophanates and / or uretdiones, cycloaliphatic Use di- and / or polyisocyanates.

(Cyclo) aliphatic Di- and / or polyisocyanates, commonly used in the paint industry are used, for example, hexamethylene diisocyanate, Octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, Tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, Isophorone diisocyanate, 2-isocyanatopropylcyclohexylisocyanate, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,4- or 1,3- or 1,2-diisocyanatocyclohexane, 2,4- or 2,6-diisocyanato-1-methylcyclohexane, Diisocyanates derived from dimer fatty acids, such as those sold under the trade name DDI Sold by Henkel, 1,8-diisocyanato-4-isocyanatomethyl-octane, 1,7-diisocyanato-4-isocyanatomethyl-heptane or 1-isocyanato-2- (3-isocyanatopropyl) cyclohexane or mixtures of these polyisocyanates.

Suitable are also isocyanates having aromatic structural elements, in which, however, the isocyanate groups at least partially to aliphatic and / or cycloaliphatic radicals are bonded, in particular 1,3-bis (2-isocyanatopropyl-2) benzene (TMXDI).

Especially is preferred for the preparation of in the radically crosslinkable Component (KK) used oligo- and / or polyurethane (meth) acrylates at least proportionally the isocyanurate of (cyclo) aliphatic isocyanates, in particular the isocyanurate of isophorone diisocyanate and / or hexamethylene diisocyanate used. Very particular preference is given to a mixture of the isocyanurate of isophorone diisocyanate and / or the isocyanurate of hexamethylene diisocyanate and / or the biuret of hexamethylene diisocyanurate and / or 1,3-bis (isocyanatomethyl) cyclohexane and / or Dicyclohexylmethane-4,4'-diisocyanate used.

Farther those suitable in EP-B-1 144 476 on page 4, line 43, to Page 5, line 31 described higher polyisocyanates based on isocyanurates, (called a2.1 there), uretdiones (there a2.2), biurets (called a2.3 there), urethane and / or allophanate groups having polyisocyanates (called a2.4 there), Oxadiazintriongruppen having polyisocyanates (called a2.6 there) and carbodiimide or uretonimine-modified polyisocyanates (called a.2.7 there).

to Preparation of the Radically Crosslinkable Component (CC) used oligomers and / or polymers, in particular the oligo- and / or polyurethane (meth) acrylates, Beyond that preferably at least proportionally cycloaliphatic di- or polyols and / or cycloaliphatic di- and / or polyamines, in particular cycloaliphatic diols used, such as cyclohexanedimethanol, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol, hydrogenated bisphenol-A, hydrogenated Bisphenol-F and tricyclodecanedimethanol.

Especially is preferred for the preparation of in the radically crosslinkable Component (KK) used oligomers and / or polymers, in particular the oligo- and / or polyurethane (meth) acrylates, hydrogenated bisphenol-A used.

As already mentioned, can cyclic structural elements also over the use of aromatic structural elements are introduced, for example, over the proportionate use of aromatic isocyanates or trimers and / or prepolymers and / or Adducts of aromatic isocyanates, such as. B. of 1,2- 1,3- and 1,4-benzenediisocyanate, 2,4- and 2,6-tolylenediisocyanate, 4,4'-biphenylenediisocyanate, Bis (4-isocyanatophenyl) methane, 2,2-bis (4-isocyanatophenyl) propane and the positionally isomeric naphthalene diisocyanates, in particular the technical mixtures of 2,4- and 2,6-Tolyulendiisocyat. Further examples for suitable aromatic structural units are triazine rings.

These structural units can be described, for example, by the use of tris (alkoxycarbonylamino) triazines according to the U.S. Patent 4,939,213 , of the U.S. Patent 5,084,541 and EP-A-624 577. Likewise, derivatives of the compounds mentioned can be used.

It is also Essential to the invention that the radically crosslinkable component (KK) at least one aliphatic structural element having at least 6 carbon atoms, preferably having 6 to 18 carbon atoms, more preferably with 6 C atoms, in the chain.

These Structural elements have a flexibilizing effect on the component (KK). With increasing content of aliphatic structural elements with at least 6 C-atoms in the chain in the component (KK) is therefore the property worsens that the dried but not yet fully cross-linked transparent coating (KT) no longer flows and of any applied Protective film no longer embossed becomes.

Farther is the chemical resistance of the lower the cross-linked transparent coating, the better the content of aliphatic structural elements having at least 6 C atoms is in the chain.

Prefers the free-radically crosslinkable component (KK) has 3 to 30% by weight, preferably 5 - 25 Wt .-%, particularly preferably 8 - 20 Wt .-%, each based on the weight of component (KK) (but of course without non-reactive components, such as. As solvents, water or additives), aliphatic Structural elements with at least 6 carbon atoms in the chain.

to introduction suitable for component (KK) are all longer-chain hydrocarbon chains.

The introduction this aliphatic structural element having at least 6 C atoms in the chain in the reactive component (KK) is carried out by use corresponding compounds with this aliphatic structural element with at least 6 C atoms in the chain for the preparation of the component (KK). In particular, you can for the preparation of urethane (meth) acrylates di- and / or polyisocyanates and / or chain extenders (Di- or polyols, di- or polyamines, di- or polythiols, di- and / or polycarboxylic etc.) with this aliphatic structural element having at least 6 C atoms are used in the chain. Particularly preferred Di- and / or polyols and / or di- and / or polycarboxylic acids and / or Di- and / or polyisocyanates with this aliphatic structural element used with at least 6 C atoms in the chain.

Suitable are, for example, dimeric and / or trimeric fatty acids for Modification of the diisocyanate and / or polyisocyanate.

Especially is preferably introduced into the radically crosslinkable component (KK) this aliphatic structural element with at least 6 C atoms in the chain through the use of appropriately functionalized derivatives of the hexamethylene, in particular by using compounds based on hexamethylene, which additionally has at least 1, preferably at least 2, isocyanate groups or OH and / or NH and / or SH- Groups, in the preparation of the oligo- and / or polyurethane (meth) acrylates.

For example hexamethylene diisocyanate and / or isocyanate-functional can be used Tri- or polymers and / or isocyanate-functional adducts of hexamethylene diisocyanate, in particular the biuret and / or the isocyanurate of the hexamethylene diisocyanate. It is also possible to use hexamethylenediol and / or hexamethylenediamine or similar Links. Possible is finally also the use of compounds other than at least 1 ethylenic unsaturated Double bond and at least 1 reactive group opposite to isocyanate groups or OH groups or NH groups is reactive, nor this aliphatic structural element having at least 6 carbon atoms in the chain, such as. B. hydroxyhexyl acrylate.

Corresponding is also a flexibilization of the polyether (meth) acrylates and the Polyester (meth) acrylates, for example, possible in that corresponding OH-functional prepolymers or oligomers (polyether or polyester base) with longer-chained, aliphatic dicarboxylic acids, in particular aliphatic dicarboxylic acids having at least 6 C atoms, such as Adipic acid, sebacic acid, dodecanedioic acid and / or dimer fatty acids, be implemented. This flexibilization reaction can be used or after the addition of acrylic or methacrylic acid to the Oligomers or prepolymers carried out become. Flexibilization of the epoxy (meth) acrylates is, for example analogous thereby possible, that corresponding epoxy-functional prepolymers or oligomers with longer-chain, aliphatic dicarboxylic acids, in particular aliphatic dicarboxylic acids having at least 6 C atoms, such as adipic acid, sebacic acid, dodecanedioic acid and / or dimer fatty acids be implemented. This flexibilization reaction can be used or after the addition of acrylic or methacrylic acid to the Oligomers or prepolymers are carried out.

As stated above, the flexibilization of the polyether (meth) acrylates or of the polyester (meth) acrylates or of the epoxy (meth) acrylates, ie an increasing content of aliphatic structural elements having at least 6 C atoms in the chain, leads to that the property is deteriorated that the dried, but not yet cross-linked transparent coating (KT) no longer flows and no longer ge of an optionally applied protective film ge is imprinted.

Farther is the chemical resistance of the lower the cross-linked transparent coating, the better the content of aliphatic structural elements having at least 6 C atoms is in the chain.

It is finally for the present invention essential that the radically crosslinkable component (KK) carbamate and / or biuret and / or Allophanate and / or urea and / or amide groups. Especially preferably contains the Component (KK) biuret and / or allophanate groups.

ever higher the Content of carbamate and / or biuret and / or allophanate and / or urea and / or Amide groups, the lower the tendency of the dried, but not yet cross-linked clearcoat (KT) to flow.

ever higher the Content of carbamate and / or biuret and / or allophanate and / or urea and / or Amide groups, the better the properties in general the end-crosslinked transparent coating (KE).

All the content of carbamate and / or biuret and / or allophanate and / or urea and / or amide groups adjusted via the Type and amount of isocyanate adducts or isocyanate prepolymers used.

Prefers indicates the radically crosslinkable component (KK) average Content of carbamate and / or biuret and / or allophanate and / or Urea and / or amide groups of more than 0 to 2.0 mol per 1000 g reactive component (KK), preferably a content of 0.1 to 1.1 mol and more preferably a content of 0.2 to 0.7 mol per 1000 g of reactive component (KK), the values in each case based on the weight of the radically crosslinkable component (KK), but of course without non-reactive components, such as. As solvents, water or additives.

The crosslinkable coating (K) preferably contains 30.0 to 99.9 Wt .-%, particularly preferably 34.0 to 69.9 wt .-% and most preferably 38.8 to 59.5 wt .-%, each based on the total weight of Coating agent (K), the component (KK).

Preferably contain the crosslinkable coating (K) at least one Initiator of chemical crosslinking. Preferably, these are initiators Photoinitiators. Preferred is the photoinitiator or the photoinitiators from the group consisting of unimolecular (Type I) and bimolecular (Type II) photoinitiators selected. Especially the photoinitiators of type I are preferably selected from the group consisting of benzophenones in combination with tertiary amines, Alkylbenzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone and halogenated benzophenones, and the Type II photoinitiators from the group consisting of benzoins, Benzoin derivatives, in particular benzoin ethers, benzil ketals, acylphosphine oxides, in particular 2,4,6-trimethylbenzoyldiphenylphosphine oxide and ethyl 2,4,6-trimethylbenzoylphenylphosphinate, Bisacylphosphine oxides, phenylglyoxylates, camphorquinone, alpha-aminoalkylphenones, alpha, alpha-dialkoxyacetophenones and alpha-hydroxyalkylphenones.

If the coating compositions are crosslinked exclusively or additionally by thermal crosslinking, they preferably contain C-C-initiating initiators, preferably benzopinacols. Examples of suitable benzopinacols are benzpinacol silyl ethers or the substituted and unsubstituted benzopinacols, as described in the American patent US 4,288,527 A in column 3, lines 5 to 44, and WO02 / 16461, page 8, line 1, to page 9, line 15 are described. Benzopinacol silyl ethers, in particular mixtures of monomeric and oligomeric benzpinacol silyl ethers, are preferably used.

Of the Content of the crosslinkable coating agent (K) on the initiators can vary widely and depends on the requirements of the In each case and the performance characteristics that the to have coatings produced therefrom (KE). Preferably the content is 0.1 to 10, in particular 1.0 to 7.0 wt .-%, in each case based on the solids of the coating agent (K).

Furthermore can the crosslinkable coating compositions (K) conventional and known additives contained in effective amounts. Usually the amount is these additives between 0 and 10 wt .-%, preferably between 0.2 and 5.0 wt .-%, each based on the solids of the Coating agent (K). Preferably, they are from the group, consisting of light stabilizers, such as UV absorbers and reversible radical scavengers (NECK); antioxidants; Wetting agents; emulsifiers; slip additives; polymerization inhibitors; Adhesion promoters; Leveling agents; film-forming tools; rheological; Flame retardants; Corrosion inhibitors that are no pigments; anti-caking agents; To grow; driers; biocides and matting agents selected.

Examples of suitable additives are described in detail in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, in D. Stoye and W. Freitag (Editors), in the German patent application DE 199 14 896 A1 , Column 14, line 26, to column 15, line 46, or in the German patent application DE 199 08 018 A1 , Page 9, line 31, to page 8, line 30 described.

The Crosslinkable coating agents (K) generally still contain conventional solvents and / or water but also substantially or completely free of solvents and essentially or completely be formulated free of water as so-called 100% systems. If the Coating agent (K) Solvent contain, then they contain preferably 20 to 70 wt .-%, especially preferably from 30 to 64.5% by weight and most preferably from 40 to 60 wt .-%, each based on the total weight of the coating composition (K), one or more solvents and / or water, preferably one or more organic solvents.

Suitable solvents are all solvents customarily used in clearcoats, in particular alcohols, glycol ethers, esters, ether esters and ketones, aliphatic and / or aromatic hydrocarbons, for example acetone, methyl isobutyl ketone, methyl ethyl ketone, butyl acetate, 3-butoxy-2-propanol, ethylethoxypropionate, butylglycol, dipropylene glycol methyl ether , glycolate, Shellsol ^® T, Pine oil 90/95, solvent naphtha ^®, Shellsol ^® A, gasoline 135/180 etc.

Prefers contains the crosslinkable coating composition (K) less than 20 wt .-%, in particular less as 10% by weight, more preferably less than 5% by weight, respectively based on the weight of the component (KK), and especially does not prefer a polymeric, saturated Component (KS), in particular no thermoplastic polymers.

methodical the preparation of the coating agent (K) has no special features but is done by mixing and homogenizing the components described above by means of customary and known mixing methods and devices such as stirred tanks, Agitator mills, kneaders, Ultraturrax, inline dissolver, static mixers, sprocket dispersers, Pressure relief nozzles and / or Microfluidizer, preferably with the exclusion of actinic radiation.

The Transparent coating is usually in such amount applied, that a dry film thickness of at least 30 microns, preferably a dry film thickness of 30 to 160 μm, more preferably 40 up to 80 μm, results.

Pigmented coating agent (P)

When pigmented coating compositions (P) become solvent-based or aqueous coating compositions (P), which are generally physical or thermal and / or curable with actinic radiation are.

• (I) ein oder mehrere Lösemittel und/oder Wasser
• (II) ein oder mehrere Bindemittel, bevorzugt ein oder mehrere Polyurethanharze und/oder Acrylatharze, besonders bevorzugt eine Mischung aus mindestens einem Polyurethanharz und mindestens einem Acrylatharz,
• (III) ggf. mindestens ein Vernetzungsmittel
• (IV) ein oder mehrere Pigmente sowie
• (V) ggf. ein oder mehrere übliche Hilfs- und Zusatzstoffe

The pigmented coating agents (P) used usually contain

• (I) one or more solvents and / or water
• (II) one or more binders, preferably one or more polyurethane resins and / or acrylate resins, particularly preferably a mixture of at least one polyurethane resin and at least one acrylate resin,
• (III) optionally at least one crosslinking agent
• (IV) one or more pigments as well
• (V) optionally one or more customary auxiliaries and additives

Prefers become the usual and known, physically and / or thermally curable, conventional or aqueous Basecoats (P) are used, as for example from the WO 03/016095 A 1, page 10, line 15, to page 14, line 22, or in particular from US-A-5, 030, 514, column 2, line 63, to column 6, line 68 and column 8, Line 53 to column 9, line 10 and EP-B-754 740, column 3, line 37, to column 6, line 18, are known.

All particularly preferred are thermally curable aqueous basecoats (P) used.

When Binder suitable are those in basecoats in the field of Automotive industry usually polyurethane resins and acrylate resins used, those skilled in the art known way over the choice of the type and amount of preparation of these binders used structural components in particular the flexibility and thus the suitability of the binder for the inventive method is controlled. In terms of For details, see, for example, US-A-5,030,514, column 2, line 63, to column 6, line 68 and column 8, line 53 to column 9, line 10.

Furthermore The pigmented coating agents preferably still contain as crosslinking agents at least one aminoplast resin. Suitable are in principle the im Field of the paint industry usually used aminoplast resins, wherein the reactivity of the aminoplast resins the properties of the pigmented coating agents are controlled can.

The content of binder and optionally amino resin in the pigmented coating composition can be varied widely and is usually two at 0 to 70 wt .-%, preferably 10 to 60 wt .-%, polyurethane resin, 0 to 70 wt .-%, preferably 10 to 60 wt .-%, acrylate resin and 0 to 45 wt .-%, preferably 5 to 40 wt .-%, aminoplast resin, in each case based on the total amount of binder plus aminoplast resin.

Based on the total weight of the pigmented coating agent (P) is the proportion of binder plus, if appropriate, aminoplast resin usually 10 to 50% by weight.

The pigmented coating agent (P) also contains at least one pigment. Preferably, the pigment is selected from the group consisting of organic and inorganic, coloring, effect, color and effect, magnetically shielding, electrically conductive, corrosion-inhibiting, fluorescent and phosphorescent pigments selected. Preferably the color and / or effect pigments used.

Examples of suitable effect pigments, which may also be coloring, are metal flake pigments, such as commercial aluminum bronzes, according to DE 36 36 183 A1 chromated aluminum bronzes, and commercial stainless steel bronzes, and non-metallic effect pigments, such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide or liquid-crystalline effect pigments. In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 176, "Effect pigments" and pages 380 and 381 "Metal oxide mica pigments" to "Metallic pigments".

suitable Organic and / or inorganic coloring pigments are those in the paint industry usually used pigments.

Of the Content of the coating agent (P) on the pigments can be very broad vary and depends primarily on the depth of color and / or the intensity the effect to be adjusted, as well as the dispersibility of the pigments in the coating compositions (P). Preferably lies the pigment content, in each case based on the coating agent (P), at 0.5 to 50, preferably 1 to 30, particularly preferably 2 to 20 and in particular 2.5 to 10 wt .-%.

Except the The pigments described above may be the coating agent (P) usual and known auxiliaries and additives, such as organic and inorganic, transparent and opaque fillers and nanoparticles and other common Auxiliaries and additives in usual Amounts, preferably 0 to 40 wt .-%, based on the coating composition (P), contain.

The pigmented coating (P) is usually in such amount applied, that a dry film thickness of at least 30 microns, preferably a dry film thickness of 30 to 160 μm, more preferably 50 up to 150 μm, results.

Thermoplastic carrier film (T)

The thermoplastic carrier film (T) may be monolayer or at least one more layer include.

So can (T) on the later Coating (B) facing away from (T2) at least one adhesive layer (HS). However, the side (T2) of the carrier film is preferred directly without interlayer connected to the plastic compound (KM).

Between the surface (T1) and the later Coating (B) can still be at least one, in particular one, Interlayer (ZS), such as. B. Filler layer (FS) and / or primer layer (HS) are located. It can or can yourself between the surface (T1) and the adhesion promoter layer (HS) and / or between the adhesion promoter layer (HS) and the coating (B) at least one, in particular a, transition layer (ÜS) are located. Preferably, however, the coating (B) is direct, ie without intermediate layer, on the surface (T1) arranged.

The support film (T) consists essentially or wholly of at least one thermoplastic polymer. Preferably, the thermoplastic polymer is selected from the group consisting from usual and known, linear, branched, star-shaped comb-shaped and / or block-like structure Homo- and copolymers, selected. The homoge- and copolymers of the group consisting of polyurethanes, Polyesters, especially polyethylene terephthalates and polybutylene terephthalates, Polyethers, polyolefins, polyamides, polycarbonates, polyvinyl chlorides, Polyvinylidene fluorides, poly (meth) acrylates, in particular polymethyl methacrylates and polybutyl methacrylates and impact modified polymethylmethacrylates, Polystyrenes, in particular impact-modified polystyrenes, especially Acrylnitrilbutadienstyrolcopolymeren (ABS), Acrylstyrolacrylonitrile copolymers (ASA) and acrylonitrile-ethylene-propylene-diene-type copolymers (A-EPDM); Polyetherimides, polyetherketones, polyphenylene sulfides, polyphenylene ethers and mixtures of these polymers.

ASA is generally understood as meaning impact-modified styrene / acrylonitrile polymers in which graft copolymers of vinylaromatic compounds, in particular styrene, and of vinyl cyanides, in particular acrylonitrile, on polyalkyl acrylate rubbers in a copolymer matrix of, in particular, styrene and acrylonitrile.

With Particular advantages are ASA, polycarbonates, blends of ASA and Polycarbonates, polypropylene, polymethyl methacrylates or impact-modified Polymethyl methacrylates, in particular blends of ASA and polycarbonates, preferably with a polycarbonate content> 40%, in particular> 50% used.

For the carrier film (T) preferably used materials are also in particular the in DE-A-101 13 273 on page 2, line 61, to page 3, line 26 described thermoplastic polymers.

The Homopolymers and copolymers can the usual in the field of thermoplastics and known additives. In addition, it could be customary and known fillers, reinforcing fillers and fibers. Last but not least, they can also use the pigments including Effect pigments and / or usual and known dyes, and thus a hue adjustment of carrier films to the hue of the pigmented coating materials (P) allow obtained coating.

The Layer thickness of the carrier film (T) is usually at more than 0.5 mm, preferably between 0.7 and 2.0 mm and especially preferably between 0.9 and 1.2 mm.

As transition layers (ÜS) can be usual and known, preferably 1 to 50 microns thick layers of thermoplastic materials, in particular used from the thermoplastic polymers described above become.

The Primer layer is used when the adhesion between the carrier film (T) and the plastic mass (KM) is insufficient, for example, if for (T) or (KM) polyolefins are used. As a primer layer (HS) can be common and known, such. B. in DE-A-101 13 273 on page 4, lines 27 to 29 described, preferably 1 to 100 microns thick layers of conventional Adhesion promoters are used.

Plastic material (KM)

Preferably contains the liquid or softened plastic material (KM) at least one molten one or softened, thermoplastic polymer, in particular at least one of the above in the carrier film (T) described thermoplastic polymers, or it consists of this.

Prefers are used plastic materials containing fibers, wherein under fibers also platelet-shaped products to be understood. examples for suitable fibers are carbon aramid steel or glass fibers, aluminum flakes, preferably glass fibers.

For example are also in DE-A-101 13 273 on page 4, line 44, to Page 5, line 45 described plastic materials.

The Process variant in which such a molten or softened, thermoplastic polymer is also used as a back injection (»injection molding ") or Hinterpressen referred.

at the liquid or softened plastic material can also be a usual and known reactive Act mixture in the mold or backfill tool the solid plastic material (KM) forms. The plastic material (KM) can also do the above in connection with the support film (T) additives described. Furthermore, plastic materials can also be used (KM) are used, which contain pore-forming propellants. examples for suitable reactive Mixtures are usually those in the backfoaming process used known reactive mixtures, in particular polyurethane foams, e.g. those in EP-B-995 667, in particular EP-B-995 667, column 2, line 40, to column 3, line 14; Column 5, lines 23 to 29; Column 8, Lines 33 to 38 described reactive mixtures.

The Process variant in which such a reactive mixture or blowing agent-containing mixture (KM) is used, too as a backfoaming ( "Reaction injection molding " RIM).

Protective film (S)

When Protective film (S) are suitable all commonly used protective films, which may be single or multi-layered. In particular, the in DE-A-10335620, page 17, line 20, to page 19, line 22, described protective films used.

Suitable are in particular protective films (S) based on homopolymers and copolymers of polyethylene, polypropylene, ethylene copolymers, propylene copolymers and ethylene-propylene copolymers.

The protective film is preferably selected such that it has a thickness of 50 μm Transmission> 70% for UV radiation and visible light has a wavelength of 230 to 600 nm.

Furthermore, it is preferred to use protective films which have a storage modulus E 'of at least 10 ⁷ Pa in the temperature range from room temperature to 100 ° C. and an elongation at break of> 300% at 23 ° C., longitudinally and transversely to the preferred direction produced during the production of the protective film by means of directed production methods. exhibit. In addition, the side of the protective film facing the coating (B) particularly preferably has a hardness <0.06 GPa at 23 ° C. and a roughness determined with the aid of atomic force microscopy (AFM), corresponding to an R _a value of 50 μm ² < 30 nm, up.

All the protective films (S) are particularly preferably 10 to 100 μm, in particular 30 to 70 μm, thick.

The Protective films to be used according to the invention (S) are common and known and are, for example, by the company Bischof + Klein, D-49525 Lengerich, under the designation GH-X 527, GH-X 529 and GH-X-535.

method for the production of molded parts

Process step I

The pigmented coating agent (P) may be in one or two or more layers on the thermoplastic support film be applied.

Becomes the pigmented coating agent (P) applied in only one layer, this is preferably done by means of a non-directed application method, that in the resulting pigmented coatings no arrangement causes the pigments in a preferred direction. That is, the pigments are distributed isotropically in the coating. Examples of suitable non-directed application methods and devices therefor are out WO 03/016095 A1, page 20, line 4, to page 23, line 25, known. In particular, pneumatic or electrostatic Spraying devices used, as described in WO 03/016095 A1, page 20, line 4, to page 23, line 25 are described.

Becomes the pigmented coating agent (P) in two or more layers applied, this is preferably done by the first - or at a total of more than 2 pigmented layers - the first layers with Help of a directed application procedure, which in the resulting pigmented Coating an arrangement of the pigments in a preferred direction, d. h., Anisotropic distribution of the pigments causes applied will or will be. Examples of suitable directed application methods are known from WO 03/016095 A1, page 15, lines 6 to 19, known. In particular, doctor blades, casting devices and rollers used. The last pigmented layer is then by means of the non-directed application method described above applied.

The Coating agent (K) may also be present in one or more layers, preferably in a layer, with the aid of those described above directed and non-directed application method applied become. Preferably, the coating agent (K) is directed Application method applied, very preferably with extrusion foundries. Prefers become the coating agent (K) excluding actinic Radiation applied and processed further.

in the Generally, too in the case of multi-layer application of the pigmented coating agent (P) before application of the next layer of the pigmented coating agent briefly flashed off, preferably at an elevated temperature. As well is applied before applying the coating agent (K) previously applied pigmented coating (P) briefly flashed off, preferably at an elevated temperature. This airing becomes common also called conditioning.

It but it is essential that the applied coating agent (K) dried after its application and before process step II and / or partially cross-linked, whereby a not yet cross-linked Coating (KT) is generated.

The coating thus obtained (KT) must not flow and not be embossed by an optionally applied protective film. This ensures that that moldings are obtained in their film-side appearance meet the requirements for a so-called Class A surface.

For drying or conditioning the wet pigmented coatings as well The wet transparent coatings are preferably thermal and / or convection methods using conventional and known devices, like continuous furnaces, NIR and IR radiant heaters, blowers and blast tunnels, be used. These devices can also be combined with each other.

Usually, the drying or conditioning of the transparent coating takes place in such a way that the coating is flashed off at ambient temperature (generally 25 ° C.) for a time of 2 to 30 minutes and then at elevated temperature (preferred oven temperature of 80 to 140 ° C.) a time of 5 to 30 minutes is dried.

Regarding one preferably used method for application and drying the pigmented coating agent (P) and the coating agent (K) is also on the not yet published German patent application with the file number 10 2004 010 787.4, page 16, line 4, to page 25, Line 8, referenced.

• a. das pigmentierte Beschichtungsmittel (P) auf die Trägerfolie aufgetragen wird, wodurch eine nasse pigmentierte Schicht 1a resultiert, die auf einen Restgehalt an flüchtigen Substanzen von x < 10 Gew.-%, bezogen auf die pigmentierte Schicht, eingestellt wird, wodurch eine konditionierte pigmentierte Schicht 1b resultiert,
• b. der Verbund aus Trägerfolie und konditionierter Schicht 1b auf eine Temperatur von < 50°C, bevorzugt < 35°C, an der Oberfläche der Schicht 1 b eingestellt wird,
• c. gegebenenfalls ein zweites pigmentiertes Beschichtungsmittel (P) oder dasselbe pigmentierte Beschichtungsmittel (P) zum zweiten Mal auf die konditionierte und temperierte Schicht 1 b aufgetragen wird, wodurch eine nasse pigmentierte Schicht 2a resultiert, die auf einen Restgehalt an flüchtigen Substanzen von y < 10 Gew.-%, bezogen auf die pigmentierte Schicht, eingestellt wird, wodurch eine konditionierte Schicht 2b resultiert,
• d. gegebenenfalls der Verbund aus Trägerfolie und konditionierten Schichten 1 b und 2b auf eine Temperatur von < 50°C, bevorzugt < 35°C, an der Oberfläche der Schicht 2b eingestellt wird,
• e. das vernetzbare Beschichtungsmittel (K) auf die konditionierte und temperierte Schicht 1 b oder 2b aufgetragen wird, wodurch eine nasse Schicht 3a resultiert, die auf einen Restgehalt an flüchtigen Substanzen von z < 5 Gew.-%, bezogen auf die Schicht des Beschichtungsmittels (K), eingestellt wird, wodurch eine konditionierte, verformbare, thermisch und/oder mit aktinischer Strahlung härtbare Schicht 3b resultiert.

The application and conditioning of the pigmented coating agent (P) and of the crosslinkable coating agent (K) is thus particularly preferably carried out in such a way that

• a. the pigmented coating agent (P) is applied to the carrier film, thereby resulting in a wet pigmented layer 1a adjusted to a residual volatile content of x <10% by weight of the pigmented layer, thereby forming a conditioned pigmented layer 1b results,
• b. the composite of carrier film and conditioned layer 1b is adjusted to a temperature of <50 ° C., preferably <35 ° C., at the surface of the layer 1b,
• c. optionally a second pigmented coating composition (P) or the same pigmented coating composition (P) is applied to the conditioned and tempered layer 1b for the second time, resulting in a wet pigmented layer 2a which has a residual volatile content of y <10% by weight. %, based on the pigmented layer, which results in a conditioned layer 2b,
• d. if appropriate, the composite of carrier film and conditioned layers 1 b and 2 b is adjusted to a temperature of <50 ° C, preferably <35 ° C, at the surface of the layer 2 b,
• e. the crosslinkable coating agent (K) is applied to the conditioned and tempered layer 1 b or 2b, resulting in a wet layer 3 a, which has a residual volatile content of z <5 wt .-%, based on the coating agent layer (K ), thereby resulting in a conditioned, deformable, thermally and / or actinic radiation curable layer 3b.

This process is particularly preferably carried out in such a way that in process step a
in the first drying section an average drying rate of 10 to 40 wt .-% / min, based on the total content of volatile substances of the applied pigmented layer, to a residual content of volatile substances of x = 12 to 30 wt .-%, based on the pigmented Layer, is reached, and
in the last drying section, an average drying rate of 1 to 6% by weight / min, based on the total volatile substance content of the applied pigmented layer, to a residual volatile content of x <10% by weight, particularly preferably <7% by weight. %, in particular <5 wt .-%, in each case based on the pigmented layer is reached,
and / or in process step c
in the first drying section, an average drying rate of 10 to 40 wt .- / min, based on the total volatile content of the applied layer, to a residual content of volatile substances of y = 12 to 30 wt .-%, based on the pigmented layer , is reached, and
in the last drying section an average drying rate of 1.5 to 4 wt .- / min, based on the total content of volatile substances of the applied pigmented layer, to a residual content of volatile substances of y <10 wt .-%, particularly preferably <7 wt .-%, in particular <5 wt .-%, in each case based on the pigmented layer is reached,
and / or in process step e
in the first drying section, an average drying rate of 10 to 30 wt .- / min, based on the total volatile content of the applied layer of the coating agent (K), to a residual volatile content of z = 10 to 15 wt .-%, based on the layer of the coating agent (K), is reached, and
in the last drying section an average drying rate of 0.5 to 3% by weight / min, based on the total volatile content of the applied layer of the coating agent (K), to a residual volatile content of z <7% by weight, especially preferably <5% by weight, in particular <3% by weight, in each case based on the layer of the coating agent (K),
applies.

With the process step e is preferably the not yet cross-linked Coating (KT) obtained.

The in the course of the process according to the invention resulting composites of carrier film and pigmented layer can wound up before the application of the next layer, stored, transported and another application device supplied where they are with this next one Layer to be coated. For this purpose, the composites with protective film are covered, which deducted again before the application of the next layer become.

Preferably, however, the process according to the invention is carried out in a continuous plant which contains all the necessary application devices and conditioning devices. In addition, this continuous plant contains conventional and known devices for the supply of pigmented and transparent Be coating means to the application devices, unwinding devices for the carrier films and protective films and winders for the multilayer films F, driving devices for the BeWe movement of the films and optionally the application devices, suction devices for the volatile substances, cooling fans and / or cooling rollers for adjusting the surface temperature of the conditioned lacquer layers , Measuring and control devices and optionally devices for the shielding of actinic radiation.

steps II to IV

In front the process step II is the above-described in step I. produced, film (F) is preferably in an open Molding tool, in particular a deep-drawing tool or a thermoforming tool, inserted. For this purpose, the film (F) can be wound from a roll and cut into suitably sized pieces. After that, the Foil (F) or the cut pieces - especially in the thermoforming tool or thermoforming tool - preformed, especially adapted to the contours of the backfill tools. These three-dimensionally preformed pieces are then in the process step II in a tool, in particular in a back-feeding tool, inserted.

It but it is also possible the film (F) or cut pieces of the film (F) directly, i. without previous three-dimensional deformation, in the process step II in a tool, in particular a back-feeding tool or molding tool, insert and deform directly in this tool.

in the Step III, the tool is closed, and the the surface (T1) opposite side (T2) of the thermoplastic carrier film (T) comes with a liquid or softened plastic material (KM), causing the coated thermoplastic carrier film (T) possibly formed and adhesively bonded to the plastic material (KM) becomes. Subsequently you leave that Plastic material (KM) solidify.

in the Process step IV becomes that in stage III. obtained molding the Tool removed. It can then be further processed immediately or until implementation of the process step V are stored.

The Process steps II to IV are known to the person skilled in the art and also described in a variety of references. exemplary be here only on DE-A-101 13 273, page 5, line 47, to page 7, Line 35, referenced.

step V

in the Process step V, the coating (KT) is finally cross-linked. This takes place at any time in the course of the procedure. The networking can also take place in two or more steps, so that - if necessary in connection to one or more partial hardenings- the final crosslinking takes place. Optionally, in this process step also the pigmented coating (P) crosslinked or postcrosslinked.

As already described during the drying of the transparent coating (KT), it is essential to the invention that the coating (KT) is not yet However, it is end-linked that (KT) is at the same time such a resistance that she no longer flows, and that she flows through a possibly applied protective film is not embossed.

These Non-crosslinked coating (KT) can be used in process step (I) and / or after the process step (I) and / or in the process step (III) and / or after the process step (IV) are cross-linked.

The but not yet cross-linked transparent coating (KT) has but an improved compared to the final cross-linked coating (KE) thermoformability on. Preferably, therefore, the coating (KT) after deformation, in particular after the adaptation of the film (F) to the contour of the film Tool in which the film (F) in step (II) inserted is, cross-linked. But since the not yet cross-linked transparent Coating (KT) one compared to the final cross-linked coating (KE) has reduced mechanical strength and in the back molding already due to the usual One of the highest possible applied high pressures high load capacity desired is to damage to avoid the film (F) and thus to ensure the required Class A surface, is it as well preferably, the final cross-linking before the back molding, ie before the Process step (III), in particular also before process step (II), but after thermoforming and / or after deep drawing, perform.

Further Is it possible, the process step V at an elevated temperature, preferably at a temperature between 25 and 150 ° C, in particular between 40 and 120 ° C and most preferably between 50 and 100 ° C to perform. The elevated temperature can by targeted heating, for example by means of IR radiators, heated air or other usual Devices are achieved. But it is also possible to process step V immediately after perform the process step IV and so caused by the injection of the back temperature increase exploit.

Preferably the final cross-linking of the coating agent (K) takes place by means of high-energy radiation, in particular by means of UV radiation. Particularly preferred is the Final crosslinking as in WO 03/016095 A1, page 27, lines 19, to Page 28, line 24, described. But it is also possible that Final crosslinking exclusively or additionally for radiation curing thermally perform. The thermal end crosslinking is preferably carried out during and / or immediately after the process step IV, so as to be caused by the injection of the back temperature increase exploit.

Preferably, in the final crosslinking by means of radiation, a radiation dose of 100 to 6,000, preferably 200 to 3,000, preferably 300 to 2,500 and particularly preferably 500 to 2,000 mJcm ^{-2 is} used, the range <2,000 mJcm ^{-2 being} very particularly preferred.

The Irradiation can be carried out under an oxygen-depleted atmosphere. "Oxygen depleted" means that the Content of the atmosphere oxygen is less than the oxygen content of air (20.95 Vol .-%). The atmosphere can basically be oxygen-free, d. h., it is to an inert gas. Because of the lack of inhibitory effect of oxygen but this can cause a strong acceleration of radiation curing, causing inhomogeneities and stresses arise in the crosslinked compositions of the invention can. It is therefore advantageous not to have the oxygen content of the atmosphere to lower to zero vol .-%.

use the molded parts

The according to the inventive method obtained moldings are extraordinary widely applicable. So can They are excellently suited as internal or external body components, as components for the ship's and aircraft construction, as components for Rail vehicles or as components for household and electrical appliances, for buildings, Windows, doors, Furniture and utensils of any kind Art be used. They are preferred as body interior or -außenbauteile or modules, in particular of cars, trucks and buses, used.

There the moldings in their film-side appearance the requirements to meet a so-called Class A surface and usually meet requirements imposed on an automotive finish suitable They are particularly excellent as attachments for car bodies, in particular for bodies of luxury cars, such. B. for the production of roofs, tailgates, Hoods, fenders, bumpers u.ä ..

example 1

The production of organic solution a urethane acrylate (organic solution of component (KK1))

A urethane acrylate was prepared from the following constitutional components by coarsely dispersing the hydrogenated bisphenol-A in 2-hydroxyethyl acrylate at 60 ° C with stirring. To this suspension were added the isocyanates, hydroquinone monomethyl ether, 1,6-di-tert-butyl para-cresol and methyl ethyl ketone. After the addition of dibutyltin dilaurate, the batch warmed. At an internal temperature of 75 ° C was stirred for several hours, until the NCO value of the reaction mixture practically no longer changed. The optionally present after the reaction still free isocyanate groups were reacted by addition of a small amount of methanol.
104.214 g of hydrogenated bisphenol-A (corresponding to 0.87 equivalents of hydroxyl groups),
147.422 g (corresponding to 0.77 equivalents of isocyanate groups) Basonate ^® HI 100 from BASF AG = commercial isocyanurate of hexamethylene diisocyanate with an NCO content from 21.5 to 22.5% (DIN EN ISO 11909)
147.422 g (corresponding to 0.77 equivalents of isocyanate groups) Basonate ^® HB 100 from BASF AG = commercial biuret of hexamethylene diisocyanate with an NCO content from 22 to 23% (DIN EN ISO 11909)
124.994 g (corresponding to 0.51 equivalents of isocyanate groups) vestanate ^® T1890 from Degussa = commercial isocyanurate of isophorone diisocyanate with an NCO content from 11.7 to 12.3% (DIN EN ISO 11909)
131.378 g of 2-hydroxyethyl acrylate (corresponding to 1.13 equivalents of hydroxyl groups)
0.328 g of hydroquinone monomethyl ether (0.05% on solid)
0.655 g of 1,6-di-tert.-butyl-para-cresol (0.1% on solid)
Methyl ethyl ketone (70% solids)
0.066 g of dibutyltin dilaurate (0.01% on solid)
4.500 g of methanol (corresponding to 0.14 equivalents of hydroxyl groups)

• • im Mittel 4,6 ethylenisch ungesättigte Doppelbindungen pro Molekül
• • einen Doppelbindungsgehalt von 1,74 mol Doppelbindungen pro 1.000 g Urethanacrylat-Festkörper
• • im Mittel 2,2 Verzweigungspunkte pro Molekül
• • 25 Gew.-% cyclische Strukturelemente, bezogen auf den Festkörpergehalt des Urethanacrylats

The component (KK1) thus obtained has the following characteristics:

• • on average 4.6 ethylenically unsaturated double bonds per molecule
• • a double bond content of 1.74 mol double bonds per 1,000 g urethane acrylate solids
• • an average of 2.2 branch points per molecule
• 25% by weight of cyclic structural elements, based on the solids content of the urethane acrylate

The production of a UV-curable coating composition (K1)

In a suitable stirring vessel was 143.00 Parts by weight of the above-described organic solution of Submitted urethane acrylate.

To submit a mixture of 1.0 parts by weight Tinuvin ^® was 292 (commercial HALS light stabilizer from Ciba Specialty Chemicals based on a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidinyl within 30 minutes) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), 2.4 parts by weight of the commercial light stabilizer solution Tinuvin ^® 400 (commercial light stabilizer from Ciba Specialty Chemicals based on a mixture of 2- (4 - ((2-hydroxy-3-dodecyloxypropyl) oxy) -2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- (4 - ((2-hydroxy 3-tridecyloxypropyl) oxy) -2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 85% in 1-methoxy-2-propanol), 0.8 parts by weight of Lucirin ^® TPO-L (commercial photoinitiator from BASF Aktiengesellschaft, based on ethyl-2,4,6-Trimethylbenzoylphenyl-phosphinate), 2.40 parts by weight of Irgacure ^® 184 (commercial photoinitiator from Ciba Specialty Chemicals, based on 1 -Hydroxy-cyclohexyl-phenylketone) used in the form of 3.0 parts of an 80% solution in acetone, and 0.2 parts by weight of a commercial polyether-modified polydimethylsiloxane (used in the form of 1.7 parts of a commercial 12.5% solution of the polyether-modified polydimethylsiloxane in xylene / Monophenylgykol 7/2 = Byk ^® 306 the company Byk Chemie) was added under constant stirring at room temperature and adjusted with 3-butoxy-2-propanol to a solids content of 48%. Subsequently, the resulting mixture was stirred for 30 minutes at room temperature.

The production of a coated, thermoplastic carrier film 1

The carrier film is a thermoplastic film of Luran ^® S was 778 TE from BASF Aktiengesellschaft a thickness of 800 microns is used. The surface of the carrier film to be coated was subjected to a 0.5 kilowatt corona pretreatment.

The Film was coated on one side with a metallic water-based paint (color: "silver metallic"). The base coat was made with the help of a box squeegee of a width of 37 cm at a belt speed of 0.5 m / min on the carrier film applied. The application was carried out at a low air flow of 0.2 m / s, a constant temperature of 21 ± 1 ° C and a constant relative Humidity 65 ± 5% carried out. The layer thickness of the resulting wet basecoat film 1a was 100 μm. The wet basecoat 1a was for 3 minutes at this Conditions ventilated and subsequently, as on page 28, lines 4 to 23, not yet published German patent application with the file number 10 2004 010 787.4 described, up to a residual content of volatile substances of x = 4 wt .-%, based on the basecoat film, dried. The resulting Conditioned basecoat 1 b a layer thickness of about 20 microns was with chill rolls set to a surface temperature <30 ° C.

• – Ausflussrate: 100 ml/min;
• – Luftdrücke: Zerstäuberluft: 2,5 bar; Hornluft: 2,5 bar;
• – Verfahrgeschwindigkeit der Düsen so hoch, dass eine Überlappung der Sprühstrahlen von 60% resultiert;
• – Abstand Düse – Folie: 30 cm.

On the conditioned and tempered basecoat 1 b, the same basecoat was applied under the following conditions using a pneumatic spray application system:

• Outflow rate: 100 ml / min;
• - Air pressures: atomizing air: 2.5 bar; Horn air: 2.5 bar;
• - Traversing speed of the nozzles so high that an overlap of the sprays of 60% results;
• - Distance nozzle - foil: 30 cm.

The Application was at a low air flow of 0.5 m / s (vertical Flow of the Foil), a constant temperature of 21 ± 1 ° C and a constant relative Humidity 65 ± 5% performed. The Layer thickness of the resulting wet basecoat layer 2a was 50 ± 2 μm. The basecoat layer 2a was flashed under these conditions for 3 minutes and then, like on page 29, lines 12 to 30 of the not yet published German patent application with the file number 10 2004 010 787.4 described, up to a residual content of volatile substances of y = 4 wt .-%, based on the basecoat film, dried. There were the air temperature at 90 ° C, the humidity at 10g / min and the air speeds at 10 m / s. The resulting conditioned basecoat layer 2b of a Layer thickness of about 10 microns was with chill rolls set to a surface temperature <30 ° C.

The conditioning agent (K) described above was applied to the conditioned and tempered basecoat film 2b with the aid of a box wiper having a width of 37 cm. The application was carried out at a low air flow of 0.2 m / s, a constant temperature of 21 ± 1 ° C and a constant relative humidity of 65 ± 5%. The layer thickness of the resulting wet clearcoat layer 3a was 120 μm. It was flashed off under the conditions mentioned for 6 minutes and then, as described on page 30, lines 10 to 29 of the unpublished German patent application with the file number 10 2004 010 787.4, up to a residual content of volatile substances of z = 2.5 Wt .-%, based on the Clearcoat, dried. The air temperature in the oven was 119 ° C for all drying stages. The resulting dried, but not yet finally cross-linked coating (KT) a layer thickness of 60 .mu.m was set with cooling rollers to a surface temperature <30 ° C and with the protective film of polypropylene described in DE-A-10335620, Example 1 (commercial product GH-X 527 of the company Bischof + Klein, Lengerich).

The resulting multilayer film (F) was wound into a roll and stored in this form until further use.

The production of plastic moldings

The multilayer film (F) was preformed. Subsequently was the transparent, not yet cross-linked coating by the Protective film partially crosslinked with UV radiation. As a positive form became a cube used. The resulting preformed part became a back injection tool inserted. The tool was closed and the cube became with a liquid Back-injected plastic material. The resulting plastic molding was cooled and taken from the tool. Subsequently, the partially crosslinked transparent coating with UV radiation cross-linked. After that was peeled off the protective film.

The plastic moldings produced in this way had a high-gloss surface, which was free from surface defects.

Example 2

The production of organic solution a urethane acrylate (organic solution of component (KK2))

A urethane acrylate was prepared from the following constitutional components by coarsely dispersing the hydrogenated bisphenol-A in 4-hydroxybutyl acrylate and pentaerythritol tri / tetra-acrylate at 60 ° C. with stirring. To this suspension were added the isocyanates, hydroquinone monomethyl ether, 1,6-di-tert-butyl para-cresol and butyl acetate. After the addition of dibutyltin dilaurate, the batch warmed. At an internal temperature of 75 ° C was stirred for several hours, until the NCO value of the reaction mixture practically no longer changed. The optionally present after the reaction still free isocyanate groups were reacted by addition of a small amount of methanol.
227.7 g of hydrogenated bisphenol-A (corresponding to 1.89 equivalents of hydroxyl groups),
178.2 g of 4-hydroxybutyl acrylate (corresponding to 1.24 equivalents of hydroxyl groups)
701.3 g pentaerythritol tri-tetraacrylate (OH number = 110 mg (KOH) / g, corresponding to 1.37 equivalents of hydroxyl groups)
325.69 g (corresponding to 1.71 equivalents of isocyanate groups) Basonate ^® HI 100 from BASF AG = commercial isocyanurate of hexamethylene diisocyanate with an NCO content from 21.5 to 22.5% (DIN EN ISO 11909)
325.69 g (corresponding to 1.74 equivalents of isocyanate groups) Basonate ^® HB 100 from BASF AG = commercial biuret of hexamethylene diisocyanate with an NCO content from 22 to 23% (DIN EN ISO 11909)
147.38 g (corresponding to 1.13 equivalents of isocyanate groups) of Desmodur ^® W from Bayer Material Science AG = commercial dicyclohexylmethane diisocyanate with an NCO content of ≥ 31.8%
0.953 g of hydroquinone monomethyl ether (0.05% on solid)
1.906 g of 1,6-di-tert.-butyl-para-cresol (0.1% on solid)
816.84 g of butyl acetate (corresponds to 70% solids)
0.7624 g of dibutyltin dilaurate (0.04% on solid)
17.1 g of methanol (corresponding to 0.53 equivalents of hydroxyl groups)

• • im Mittel 7,1 ethylenisch ungesättigte Doppelbindungen pro Molekül
• • einen Doppelbindungsgehalt von 2,92 mol Doppelbindungen pro 1.000 g Urethanacrylat-Festkörper
• • im Mittel 1,5 Verzweigungspunkte pro Molekül
• • 16 Gew.-% cyclische Strukturelemente, bezogen auf den Festkörpergehalt des Urethanacrylats

The component (KK2) thus obtained has the following characteristics:

• • an average of 7.1 ethylenically unsaturated double bonds per molecule
• • a double bond content of 2.92 mol double bonds per 1,000 g urethane acrylate solids
• • an average of 1.5 branch points per molecule
• 16% by weight of cyclic structural elements, based on the solids content of the urethane acrylate

The production of a UV-curable coating composition (K2)

In a suitable stirred vessel 143.00 parts by weight of the above-described organic solution of urethane acrylate (KK2) were submitted. To submit a mixture of 1.0 parts by weight Tinuvin ^® was 292 (commercial HALS light stabilizer from Ciba Specialty Chemicals based on a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidinyl within 30 minutes) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), 2.35 parts by weight of Tinuvin ^® 400 (commercial light stabilizer from Ciba Specialty Chemicals based on a mixture of 2- (4 - (( 2-hydroxy-3-dodecyloxypropyl) oxy) -2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- (4 - ((2-hydroxy-3-) tridecyloxypropyl) oxy) -2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine), 0.8 parts by weight of Lucirin ^® TPO-L (commercial photoinitiator from BASF Aktiengesellschaft, based on ethyl-2,4,6-trimethylbenzoyl-phenyl-phosphinate), 2.40 parts by weight of Irgacure ^® 184 (commercial photoinitiator from Ciba Spe cialty Chemicals, based on 1-hydroxy-cyclohexyl-phenyl ketone) and 0.40 parts by weight of Byk ^® 325 (commercial additive from Byk Chemie added based on a polyether Polymethylalkyksiloxans) with constant stirring at room temperature with 1-methoxypropyl-2-acetate to a Solid content adjusted to 51%. Subsequently, the resulting mixture was stirred for 30 minutes at room temperature.

2.2. Production of with a coating provided, thermoformable film. 2

The curable with UV radiation Coating agent (K2) was analogous to Example 1 for the preparation a provided with a coating film used.

Claims (15)

Process for the production of molded parts, in particular for use in the automotive industry, in which I. a film (F) having a coating (B) is prepared by applying to a possibly pretreated surface (T1) of a thermoplastic support film (T) 1. a pigmented 2. a crosslinkable coating composition (K) which contains a free-radically crosslinkable component (KK) and which gives a transparent coating (KE) after the final crosslinking, 3. the coating composition applied in stage 2 (3) K) is dried and / or partially crosslinked, whereby a not yet final cross-linked coating (KT) is produced, II. The film produced in step I. (F) inserts into an open tool, III. the tool is closed, the side (T2) of the thermoplastic carrier film (T) facing away from the surface (T1) is brought into contact with a liquid or softened plastic material (KM) and the plastic material is solidified, IV. V. The coating (KT) is finally cross-linked at any time in the course of the process, wherein the crosslinkable coating composition (K) contains a free-radically crosslinkable component (KK) which (i) contains one or more oligomers. and / or one or more polyurethane (meth) acrylates and (ii) contains on average more than 1 ethylenically unsaturated double bond per molecule, (iii) a number average molecular weight of 1000 to 10,000 g / mol, (iv) a double bond content of 1.0 to 5.0 mol double bonds per 1,000 g reactive component (KK), (v) on average per molecule> 1 branch point, (vi) 5-50 wt .-%, each based on the weight of component (KK), cyclic structural elements and (vii) at least one aliphatic structural element having at least 6 C atoms in the chain, characterized in that 1. the radically crosslinkable component (KK) carbamate and / or biuret and / or allophanate and / or urea contains ff and / or amide groups, and 2. a pigmented coating composition (P) is a solvent-containing or an aqueous coating agent is used. A coating (B) comprising film (F), producible, by on a possibly pretreated surface (T1) of a thermoplastic support film (T) 1. a pigmented coating agent (P) is applied becomes, 2. a crosslinkable coating agent (K), which is a radical contains crosslinkable component (KK) and that after the final crosslinking gives a transparent coating (KE), is applied, 3. the coating agent (K) to a transparent, but not yet completely cross-linked coating (KT) is dried, in which the crosslinkable coating agent (K) is a radically crosslinkable Component (KK) contains the (I) one or more oligo- and / or one or more polyurethane (meth) acrylates contains and (ii) on average more than 1 ethylenically unsaturated double bond per molecule, (Iii) a number average molecular weight of 1,000 to 10,000 g / mol, (Iv) a double bond content of 1.0 to 5.0 mol double bonds per 1,000 g reactive component (KK), (v) on average per molecule> 1 branch point, (Vi) 5-50% by weight, in each case based on the weight of component (KK), cyclic structural elements and (vii) at least one aliphatic Structural element with at least 6 C atoms in the chain having, characterized in that 1. the radically crosslinkable Component (KK) carbamate and / or biuret and / or allophanate and / or Contains urea and / or amide groups and 2. as pigmented Coating agent (P) a solvent-containing or an aqueous one Coating is used. The method of claim 1 or film according to claim 2, characterized in that the radically crosslinkable component (KK) an average content of carbamate and / or biuret and / or allophanate and / or urea and / or amide groups of more than 0 to 2.0 mol per 1000 g reactive component (KK), preferably has a content of 0.1 to 1.1 mol and more preferably has a content of 0.2 to 0.7 mol per 1000 g of reactive component (KK). Method according to one of claims 1 or 3 or film according to one of the claims 2 or 3, characterized in that the radically crosslinkable Component (KK) has more than 2 to 10.0 double bonds per molecule and / or that the radically crosslinkable component (KK) additionally aliphatic Has structural elements with 4 and / or 5 carbon atoms in the chain. Method according to one of claims 1 or 3 to 4 or foil according to one of the claims 2 to 4, characterized in that the radically crosslinkable Component (KK) as cyclic structural elements monocyclic structural elements with 4 to 8 ring members and / or di- and / or tri- and / or polycyclic Has structural elements with 7 to 18 ring members and / or that the cyclic structural elements are substituted. Method according to one of claims 1 or 3 to 5 or film according to one of the claims 2 to 5, characterized in that the radically crosslinkable Component (KK) as cyclic structural elements (i) cycloaliphatic Structural elements and / or (ii) heterocyclic structural elements, in particular heterocyclic structural elements, in which the number the heteroatoms per ring is 1 to 8 and / or in which the heteroatoms are selected from the group nitrogen and / or oxygen and / or sulfur, and or (Iii) aromatic structural elements , wherein preferably the Content of aromatic structural elements maximum 10 wt .-%, respectively based on the weight of the component (KK), is. Method according to one of claims 1 or 3 to 6 or foil according to one of the claims 2 to 6, characterized in that the radically crosslinkable Component (KK) as cyclic structural elements tricyclodecane rings and / or cyclohexane rings and / or isocyanurate rings and / or triazine rings contains wherein the cyclic structural elements may optionally be substituted. Method according to one of claims 1 or 3 to 7 or foil according to one of the claims 2 to 7, characterized in that the radically crosslinkable Component (KK) as aliphatic structural element with at least 6 C-atoms in the chain aliphatic structural elements with 6 to Contains 18 carbon atoms in the chain, especially hexamethylene chains. Method according to one of claims 1 or 3 to 8 or foil according to one of the claims 2 to 8, characterized in that the branch points of the radically crosslinkable component (KK) via the use of isocyanates with a functionality greater than 2 and / or over the Use of isocyanurate rings in the construction of the component (KK) introduced become. Method according to one of claims 1 or 3 to 9 or foil according to one of the claims 2 to 9, characterized in that the radically crosslinkable Component (KK) has been prepared using hexamethylene diisocyanate and / or Isophorone diisocyanate and / or methylene bis (4-isocyanatocyclohexane) and / or the corresponding isocyanurates and / or biurets and / or Allophanates of these isocyanates and / or using hydroxyethyl acrylate and / or 4-hydroxybutyl acrylate and / or pentaerythritol triacrylate and / or isopropylidenedicyclohexanol. Method according to one of claims 1 or 3 to 10 or film according to one of the claims 2 to 10, characterized in that the radically crosslinkable Component (KK) less than 5 wt .-%, preferably less than 1 wt .-%, in each case based on the weight of component (KK), and in particular having substantially no detectable, free isocyanate groups. Method according to one of claims 1 or 3 to 11 or foil according to one of the claims 2 to 11, characterized in that the pigmented coating agent (P) (I) one or more solvents and / or water (II) one or more binders, preferred one or more polyurethane resins and / or one or more acrylate resins and (III) optionally at least one crosslinking agent, (IV) at least one pigment as well (V) one or more common auxiliary and additives. Method according to one of claims 1 or 3 to 12, characterized characterized in that the pigmented coating agent either in only one layer by means of a non-directed application method or in 2 or more layers, in which case the last of these layers by means of a non-directed application method is applied and / or that the film (F) deep-drawn or thermoformed is or will. Molded part of one with a multilayer film provided plastic material (KM), characterized in that the plastic material (KM) with a film (F) according to one of claims 2 to 12 is provided. Use of according to a method according to one of claims 1 or 3 to 13 molded parts as internal or external body components or as components for the ship and aircraft construction or as components for household and electrical appliances.