DE102005024362A1 - Process for producing scratch-resistant hardened materials - Google Patents

Abstract

Process for the preparation of cured materials from compositions curable with actinic radiation by irradiation with UV radiation, characterized in that UV radiation of the following spectral distribution and dose is used: DOLLAR A - wavelength λ = 400 to 320 nm; Dose = 500 to 2500 mJ / cm x 2 x; DOLLAR A - Wavelength λ = 320 to 290 nm; Dose = 700 to 3000 mJ / cm x 2 x; DOLLAR A - wavelength λ = 290 to 180 nm; Dose = 100 to 500 mJ / cm x 2.

Description

Territory of invention

The The present invention relates to a novel process for the preparation from hardened Materials. Furthermore, the present invention relates to Use of the hardened materials produced by the new process for the Coating, bonding, sealing, wrapping and packaging bodies of Training means, in particular motor vehicle bodies, and Parts thereof, buildings in the interior and exterior and parts thereof, doors, Windows, furniture, Hollow glassware, Coils, containers, packaging, small parts, optical, mechanical and electrotechnical components and components for white goods.

The hardened Materials are preferably thermosetting. In the context of the present Invention become three-dimensional among thermoset materials understood cross-linked substances, in contrast to thermoplastic Materials only to a small extent or not at all the heat are deformable.

• (1) ein thermisch und mit aktinischer Strahlung härtbares Stoffgemisch verwendet, das nach seiner Aushärtung einen Speichermodul E' im gummielastischen Bereich von mindestens 10^7,5 Pa und einen Verlustfaktor tanδ bei 20°C von maximal 0,10 aufweist, wobei der Speichermodul E' und der Verlustfaktor mit der Dynamisch-Mechanischen Thermo-Analyse (DMTA) an freien Filmen mit einer Schichtdicke von 40 ± 10 μm gemessen worden sind, und
• (2) die Bestrahlung mit einer UV-Strahlung durchführt, deren Spektrum neben UV-A und UV-B einen UV-C-Anteil aufweist, der im Wellenlängenbereich von 200 bis 280 nm 2 bis 80% der relativen spektralen Strahldichte des Spektrums einer Quecksilbermitteldruckdampflampe in diesem Wellenlängenbereich hat, wobei in dem Wellenlängenbereich von 200 bis 240 nm die relative spektrale Strahldichte des UV-C-Anteils stets kleiner als die relative spektrale Strahldichte des Spektrums einer Quecksilbermitteldruckdampflampe in diesem Wellenlängenbereich ist und wobei
• (3) die Strahlendosis bei 100 bis 6.000 mJcm^–2 liegt.

A process for producing hardened materials is known from the German patent application DE 102 02 565 A1 known. In the known method, the cured materials are prepared from a thermally and actinic radiation-curable composition by heating and irradiation with UV radiation, wherein

• (1) a thermally and actinic radiation-curable composition used which has a memory modulus E 'in the rubber elastic range of at least 10 ^7.5 Pa and a loss factor tanδ at 20 ° C of not more than 0.10 after curing, wherein the storage modulus E and the loss factor has been measured with the Dynamic Mechanical Thermal Analysis (DMTA) on free films with a layer thickness of 40 ± 10 microns, and
• (2) the irradiation is carried out with a UV radiation whose spectrum in addition to UV-A and UV-B has a UV-C content, in the wavelength range of 200 to 280 nm 2 to 80% of the relative spectral radiance of the spectrum of a mercury medium pressure lamp in this wavelength range, wherein in the wavelength range of 200 to 240 nm, the relative spectral radiance of the UV-C portion is always smaller than the relative spectral radiance of the spectrum of a mercury mid-pressure lamp in this wavelength range and wherein
• (3) the radiation dose is 100 to 6,000 mJcm ^-2 .

in the The scope of the present invention is under actinic radiation electromagnetic radiation, for example near infrared (NIR), visible light, UV radiation, X-rays or gamma radiation, preferably UV radiation, as well as corpuscular radiation, for example, electron radiation, beta radiation, neutron radiation, Proton radiation and alpha radiation, preferably electron radiation, Understood. In particular, actinic radiation is understood to mean UV radiation.

• UV-A: 320 bis 400 nm
• UV-B: 320 bis 290 nm
• UV-C: 290 bis 100 nm

As is known, the spectrum of UV radiation is divided into three areas:

• UV-A: 320 to 400 nm
• UV-B: 320 to 290 nm
• UV-C: 290 to 100 nm

in the In general, the UV spectrum of UV sources is only up to a wavelength from 180-200 nm available, because the radiation of a lower wavelength through the quartz hollow body of the radiation sources is absorbed (see R. Stephen Davidson, "Exploring the Science, Technology and Applications of U.V. and E.B. Curing, "Sita Technology Ltd., London, 1999, Chapter I, »An Overview " Pages 3 to 34).

The resulting known hardened Materials have only a slight yellowing. They are scratch resistant and show only slight loss of gloss after scratching. simultaneously they have a high hardness and a high chemical resistance.

The but steadily growing demands of the market require one further improvement of the scratch resistance of the cured materials, in particular the scratch resistance when loaded in automatic car washes. In addition, must the adhesion of the cured Materials on substrates, in particular of metals, plastics and other hardened ones Materials to be further improved.

In particular, the interlayer adhesion must be maintained between layers of cured materials from below different material composition and / or function, especially in multi-layer coatings, further improved

task It is the object of the present invention to provide a novel process for the preparation from hardened To provide materials that the disadvantages of the prior art no longer but in a particularly simple and particularly reliable manner hardened Supplies materials; the advantageous requirement profile listed above fulfill and above In addition, an improved scratch resistance, especially under load in car washes, and improved adhesion to substrates, in particular of metals, Plastics and other hardened Materials include. In particular, the new process should be hardened materials provide improved interlayer adhesion between layers hardened Materials of different material composition and / or Function especially in multi-layer coatings and in particular when loaded with a jet of steam.

solution

• – Wellenlänge lambda = 400 bis 320 nm; Dosis = 500 bis 2.500 mJ/cm²;
• – Wellenlänge lambda = 320 bis 290 nm; Dosis = 700 bis 3.000 mJ/cm²;
• – Wellenlänge lambda = 290 bis 180 nm; Dosis = 100 bis 500 mJ/cm².

Accordingly, the new process for producing cured materials from actinic radiation-curable compositions (compositions) by irradiation with UV radiation has been found using ultraviolet radiation of the following spectral distribution and dose:

• Wavelength λ = 400 to 320 nm; Dose = 500 to 2,500 mJ / cm ² ;
• Wavelength λ = 320 to 290 nm; Dose = 700 to 3,000 mJ / cm ² ;
• Wavelength λ = 290 to 180 nm; Dose = 100 to 500 mJ / cm ² .

in the Following is the new process for making cured materials referred to as "inventive method".

Further Invention objects go out of the description.

Advantages of the invention

in the In view of the prior art, it was surprising and for the expert unpredictable that the task of the present invention underlying, be solved with the aid of the method according to the invention could.

Especially it was surprising that the inventive method in a particularly simple and reliable manner using known UV radiation sources, electronic, optical and mechanical components as well as irradiation facilities hardened materials in a particularly simple and particularly reliable way, especially thermoset materials that not only a low yellowing, a high hardness and a high chemical resistance but above In addition, an improved scratch resistance, especially under load in car washes, and improved adhesion to substrates, in particular Metals and plastics and other hardened materials. In particular, the process according to the invention provided hardened materials, the improved interlayer adhesion between layers of cured materials of different material composition and / or function especially in multi-layer coatings and in particular in the Load with a steam jet showed.

Yet more surprised that the inventive method with curable with UV radiation Substance mixtures of different composition are performed could. This allowed the mixtures in unexpectedly advantageous Be adapted optimally for a wide variety of uses so that they can be used with advantage as coating materials, adhesives, Sealants and raw materials used for moldings and films could become. In particular surprised in that the coating materials with particular advantage as electrodeposition paints, Ink pen, Antistonechip primers, solid-color topcoats, basecoats and clearcoats could be used.

Last but not least, the extraordinarily wide usability of the cured materials as coatings, adhesive layers, seals, molded parts and films, preferably as coatings, in particular electrodeposition coatings, surfacer coatings, antistonechip primers, solid-color topcoats, basecoats and clearcoats, was surprising. Specifically, they were outstandingly suitable for the coating, bonding, sealing and packaging of bodies of vehicles, especially motor vehicle bodies series, and parts thereof, internal and external structures and parts thereof, doors, windows, furniture, hollow glassware, coils, containers, packaging, small parts such as nuts, screws, rims or hubcaps, optical components, mechanical components, electrical components, such as winding goods (coils, stators, rotors), and components for white goods, such as radiators, appliances, refrigerator covers or washing machine covers.

Full Description of the invention

The inventive method is used to produce hardened Materials, in particular duroplastic materials, made with actinic Radiation curable Mixtures of substances (hereinafter referred to as "mixtures of substances" for the sake of brevity) by irradiation with UV radiation.

• – Wellenlänge lambda = 400 bis 320 nm; Dosis = 500 bis 2.500 und vorzugsweise 750 bis 2.000 mJ/cm²;
• – Wellenlänge lambda = 320 bis 290 nm; Dosis = 700 bis 3.000 und vorzugsweise 1.000 bis 2.200 mJ/cm²;
• – Wellenlänge lambda = 290 bis 180 nm; Dosis = 100 bis 500 und vorzugsweise 200 bis 450 mJ/cm².

According to the invention, UV radiation of the following spectral distribution and dose is used:

• Wavelength λ = 400 to 320 nm; Dose = 500 to 2,500 and preferably 750 to 2,000 mJ / cm ² ;
• Wavelength λ = 320 to 290 nm; Dose = 700 to 3,000 and preferably 1,000 to 2,200 mJ / cm ² ;
• Wavelength λ = 290 to 180 nm; Dose = 100 to 500 and preferably 200 to 450 mJ / cm ² .

• – Wellenlänge lambda = 400 bis 320 nm; Leistung = 100 bis 600 und vorzugsweise 120 bis 550 mW/cm²;
• – Wellenlänge lambda = 320 bis 290 nm; Leistung = 100 bis 600 und vorzugsweise 140 bis 550 mW/cm²;
• – Wellenlänge lambda = 290 bis 180 nm; Leistung = 20 bis 120 und vorzugsweise 30 bis 100 mW/cm².

The performance can vary widely. Preferably, UV radiation of the following spectral distribution and power is used:

• Wavelength λ = 400 to 320 nm; Power = 100 to 600 and preferably 120 to 550 mW / cm ² ;
• Wavelength λ = 320 to 290 nm; Power = 100 to 600 and preferably 140 to 550 mW / cm ² ;
• Wavelength λ = 290 to 180 nm; Power = 20 to 120 and preferably 30 to 100 mW / cm ² .

at the irradiation in the context of the method according to the invention, the distance the source of UV radiation to the surface of the mixture wide vary. Preferably the distance 20 to 250 and especially 40 to 100 mm.

The Irradiation time depends on a given dose the tape or feed rate of the substrates in the irradiation system and vice versa.

When Radiation sources for the invention to be used UV radiation can all usual and known UV lamps are used, as such, the relevant Radiate spectrum. But it can Even combinations of at least two UV lamps are used, while not the invention to be used Emit UV radiation, their spectra, however, to the invention to be used UV radiation add. Furthermore you can UV lamps are used in which the desired spectrum with the help of Filters and / or reflectors is set. There are also flashlights in Consideration.

Examples suitable flash lamps are flash lamps from the company VISIT.

Preferably are used as UV lamps mercury vapor lamps, preferably mercury, medium pressure and high pressure vapor lamps, in particular medium pressure mercury vapor lamps, used. Particularly preferred are unmodified mercury vapor lamps plus suitable filters and / or reflectors or modified, in particular doped, mercury vapor lamps used.

Examples Suitable modified mercury vapor lamps are gallium doped and / or iron-doped, in particular iron-doped, mercury vapor lamps, For example, in R. Stephen Davidson, Exploring the Science, Technology and Applications of U.V. and E.B. Curing, "Sita Technology Ltd., London, 1999, Chapter I, »An Overview " Page 16, Figure 10, or Dipl.-Ing. Peter Klamann, »eltosch Systems expertise, UV technology, guideline for User", Page 2, October 1998.

Examples suitable unmodified mercury vapor lamps plus appropriate Filters and / or reflectors are the UV lamps from Arccure. These spotlights are designed so that no UV radiation directly on the to be hardened Mixtures of substances, but only indirectly reflected radiation in two bundled strips. For both reflected stripes can different reflectors are used, covering the entire UV spectrum reflect ("wide"), the long-wave Proportion of the UV spectrum stronger on the plastic moldings reflect ("A + B") or the shortwave portion of the UV spectrum stronger to reflect on the sample ("C").

The arrangement of the radiation sources can the spatial conditions of the mixtures or the Substrates to which they have been applied, as well as the process parameters are adjusted. In complicated shaped substrates, such as those provided for automobile bodies, the non-direct radiation accessible areas (shadow areas), such as cavities, folds and other constructional undercuts, may be spot, small area or omnidirectional, coupled with an automatic agitator of cavities or edges, to be cured.

Preferably is in the context of the method according to the invention the irradiation is carried out under an oxygen-depleted atmosphere.

"Oxygen depleted" means that the Content of the atmosphere of oxygen at the surface of the Mixtures is less than the oxygen content of air (20.95 Vol .-%). Preferably the maximum content of the deoxygenated atmosphere is 18, preferably 16, more preferably 14, most preferably 10 and in particular 6.0% by volume.

The the atmosphere can be basically free of oxygen, d. h., it is a Inert gas. The complete or Extensive oxygen freedom can also be achieved by the cover the surface the mixtures are achieved with an oxygen-impermeable film.

The lack of inhibitory effect of oxygen can in these cases, however cause a strong acceleration of radiation curing, causing inhomogeneities and Stresses in the coatings of the invention can arise. It is therefore not in all cases advantageous to lower the oxygen content of the atmosphere to zero vol .-%.

Preferably the minimum content of oxygen is 0.1 and especially 0.5% by volume.

The oxygen-depleted atmosphere can be provided in different ways. Preferably a corresponding gas mixture is prepared and in pressure bottles to disposal posed. Preferably, the depletion is achieved by at least an inert gas in the respective quantities required in the above surface the one to be hardened Layered air cushion brings. The oxygen content of the above relevant surface located atmosphere can with the help of usual and known methods and apparatus for the determination of elemental Oxygen continuously measured and possibly automatically on the desired Value to be set.

Under Inert gas is understood to mean a gas which under the conditions of curing used is not decomposed by the actinic radiation, the curing is not inhibited and / or not reacted with the mixtures. Preferably are nitrogen, carbon dioxide, helium, neon or argon, in particular Nitrogen and / or carbon dioxide, used.

The in the method according to the invention used mixtures are with actinic radiation, in particular UV radiation, curable. This means that they contain ingredients or consist of ingredients, which are activatable with actinic radiation, causing them radically or ionic, especially with free-radical polymerize. hereby there is a three-dimensional cross-linking of the mixtures, whereby the hardened Materials, especially the thermoset materials, result.

In addition, the Mixtures physically and / or thermally curable.

in the In the context of the present invention, the term "physical Hardening "the hardening of the mixtures, especially in the form of a layer of a coating material, by filming by solvent release from the mixtures, with the linkage within the coating via looping the polymer molecules the binder (for the term see Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, Binders, pages 73 and 74). Or the filming takes place over the Coalescence of binder particles (see Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening," pages 274 and 275). Usually are for this no crosslinking agents necessary.

In the context of the present invention, the term "thermal curing" means the heat-initiated curing of a substance mixture, in particular a layer of a coating material, to which usually a binder and a separately present crosslinking agent is applied. If the crosslinking agents are already incorporated in the binders, this is also referred to as self-crosslinking Therefore, it is preferably used (see Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 to 276, especially page 275, below).

From Experts will find mixtures of substances with actinic radiation and thermally curable are also referred to as dual-cure substance mixtures.

Preferably, in the method according to the invention, mixtures of substances are used which, after their curing, have a storage modulus E 'in the rubber elastic range of at least 10 ^7.5 , preferably at least 10 ^7.6 , preferably at least 10 ^8.0 and in particular at least 10 ^8.3 Pa and one Loss factor tanδ at 20 ° C of a maximum of 0.10, preferably a maximum of 0.06, wherein the storage modulus E 'and the loss factor with the Dynamic Mechanical Thermal Analysis (DMTA) of free films with a layer thickness of 40 ± 10 microns have been measured.

The energy fraction (elastic portion) to be recovered in the event of deformation of a viscoelastic material, such as a polymer, is determined by the size of the storage module E ', while the energy fraction consumed in this process is described by the size of the loss modulus E ". The modules E 'and E''are dependent on the deformation rate and the temperature. The loss factor tanδ is defined as the quotient of the loss modulus E "and the storage modulus E '. tanδ can be determined by means of Dynamic Mechanical Thermal Analysis (DMTA) and provides a measure of the relationship between the elastic and plastic properties of the film. DMTA is a well-known measurement method for determining the viscoelastic properties of coatings and, for example in Murayama, T., Dynamic Mechanical Analysis of Polymeric Materials, Elsevier, New York, 1978, and Loren W. Hill, Journal of Coatings Technology, Vol. 808, May 1992, pages 31 to 33. The process conditions in the measurement of tanδ by DMTA are described by Th. Frey, K.-H. Great Brinkhaus and U. Röckrath in Cure Monitoring Of Thermoset Coatings, Progress In Organic Coatings 27 (1996), 59-66, or in the German patent application DE 44 09 715 A1 or the German patent DE 197 09 467 C2 described in detail. Preferably, the following conditions are used: Tensile mode; Amplitude: 0.2%; Frequency: 1Hz; Temperature ramp: 1 ° C / min from room temperature to 200 ° C.

Of the Memory module E 'can by the skilled artisan by selecting certain actinic radiation curable ones and optionally physically and / or thermally curable Ingredients, functionality the constituents and their proportion of the invention to be used Be set mixture.

Of the Memory module E 'can with the aid of actinic radiation curable components in the Usually be adjusted by the type and amount of ingredients preferably chosen so be that per g of solids of the substance mixture 0.5 to 6.0, preferably 1.0 to 4.0 and especially preferably 2.0 to 3.0 meq of actinic radiation activatable Bindings are present.

in the Under the present invention is under solid state the Sum of the constituents of a mixture understood that from this manufactured hardened Build up material.

in the The scope of the present invention is under a with actinic Radiation activatable bond understood a bond at Irradiation with actinic radiation becomes reactive and with others activated bonds of their type polymerization reactions and / or Crosslinking reactions that after radical and / or ionic Mechanisms expire. Examples of suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, Carbon-phosphorus or carbon-silicon single bonds or double bonds. Of these, the carbon-carbon double bonds are particularly advantageous and therefore become very particular according to the invention preferably used. The brevity In the following, they are referred to as "double bonds".

Especially preferred double bond containing compounds are acrylate groups containing compounds.

The Mixtures of substances can acid groups contain. If used, they are in abundance of more than 0.05, preferably more than 0.08, more preferably more than 0.15 and especially more than 0.2 meq / g of solids. In this case, the existing amount of acid groups 15, preferably 10, particularly preferably not exceed 8 and in particular 5 meq / g of solids.

When used, the acid groups are preferably selected from the group consisting of selected from carboxyl groups, phosphonic acid groups, sulfonic acid groups, acidic phosphate ester groups and acidic sulfate ester groups, especially carboxyl groups.

The Material composition of the inventive method to be used mixtures of substances is not critical, but it can all the usual and known, with actinic radiation, in particular UV radiation, and optionally physically and / or thermally curable Mixtures are used.

Suitable constituents of such substance mixtures, the suitable mixtures themselves and the processes for their preparation are known, for example, from the German patent application DE 102 02 565 A1 , Page 4, paragraph [0029], to page 8, [0079], or the German patent DE 197 09 467 C2 , known.

• (i) ein oder mehrere Oligo- und/oder ein oder mehrere Polyurethan(meth)acrylate enthält und
• (ii) im statistischen Mittel mehr als eine olefinisch ungesättigte Doppelbindung pro Molekül,
• (iii) ein zahlenmittleres Molekulargewicht von 1.000 bis 10.000 Dalton,
• (iv) einen Doppelbindungsgehalt von 1,0 bis 5,0 Doppelbindungen pro 1.000 g radikalisch vernetztbarer Komponente,
• (v) im statistischen Mittel pro Molekül > 1 Verzweigungspunkt,
• (vi) 5 bis 50 Gew.-%, jeweils bezogen auf das Gewicht der Komponente, cyclische Strukturelemente und
• (vii) mindestens ein aliphatisches Strukturelement mit mindestens 6 Kohlenstoffatom in der Kette

aufweist, wobei die radikalisch vernetzbare Komponente Carbamat- und/oder Biuret- und/oder Allophanat- und/oder Harnstoff- und/oder Amidgruppen enthält.The process according to the invention offers particular advantages when it is carried out with substance mixtures containing at least one radically crosslinkable or curable component which

• (i) one or more oligo- and / or one or more polyurethane (meth) acrylates containing and
• (ii) on average more than one olefinically unsaturated double bond per molecule,
• (iii) a number average molecular weight of 1,000 to 10,000 daltons,
• (iv) a double bond content of 1.0 to 5.0 double bonds per 1000 g of radically crosslinkable component,
• (v) in statistical average per molecule> 1 branch point,
• (vi) 5 to 50 wt .-%, each based on the weight of the component, cyclic structural elements and
• (vii) at least one aliphatic structural element having at least 6 carbon atoms in the chain

wherein the radically crosslinkable component contains carbamate and / or biuret and / or allophanate and / or urea and / or amide groups.

Prefers contains the radically crosslinkable component is at least 50% by weight, especially preferably at least 70% by weight and most preferably at least 80% Wt .-%, in each case based on the solids content of the free radical crosslinkable component, one or more oligourethane (meth) acrylates and / or one or more polyurethane (meth) acrylates. In particular exists the radically crosslinkable component to 100% of one or more Oligourethan (meth) acrylates and / or one or more polyurethane (meth) acrylates.

Prefers contains the radically crosslinkable component also more than 50 wt .-%, more preferably not more than 30% by weight and most preferably not more than 20% by weight, such as 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. Preference is given to polymers which in addition to the double bonds still hydroxyl, carboxyl, amino and / or thiol groups contain. In most cases Needless the use of the other radically crosslinkable components

Prefers contains while the free-radically crosslinkable component less than 5 wt .-%, preferably less than 1 wt .-%, each based on the weight the radically crosslinkable component, and in particular substantially no detectable, free isocyanate groups.

Besides that is it is preferred that the radically crosslinkable component is a mixture various oligo- and / or polyurethane (meth) acrylates, which 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 in the preparation of a corresponding oligo- or polyurethane (meth) acrylate at the same time different products are created.

to Achieving good crosslinking is preferably radically crosslinkable Components with a high reactivity of the functional groups used, particularly preferably radically crosslinkable components, 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 reactive toward isocyanate groups Contains groups Mix the components in any order, if necessary at elevated Temperature, are produced.

Prefers becomes the compound that is reactive towards isocyanate groups Contains 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 olefinically unsaturated carboxylic acids will, by what, first a part of the isocyanate groups is reacted. Below is a Chain extender from the group of diols / polyols and / or diamines / polyamines and / or Added 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 olefinic 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 olefinically unsaturated hydroxyalkyl ester and following this can the 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 carried out.

Prefers is worked under anhydrous conditions. anhydrous means that the water content in the reaction system is no longer is 5% by weight, preferably not more than 3% by weight, and more preferably not more than 1 Wt .-%. In particular, the water content is below the detection limit.

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, e.g. Double bond content, double bond equivalent weight, Content of branching points, content of cyclic structural elements, Content of aliphatic structural elements having at least 6 carbon 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 To produce urethane (meth) acrylates, 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.

Especially, when the urethane (meth) acrylates used in aqueous mixtures become part of the existing in the reaction mixtures free isocyanate groups are still reacted with compounds containing a isocyanate-reactive group, preferably selected from the group consisting from 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 or gamma-hydroxybutyric acid, in particular hydroxyacetic (Glycolic acid).

For the inventive method can the substance mixtures in the most different physical conditions and three-dimensional shapes exist.

So can the mixtures at room temperature solid or liquid or be flowable. But you can also be solid at room temperature and flowable at higher temperatures, preferably showing thermoplastic behavior. Especially can they are conventional, organic solvents containing mixtures, aqueous Mixtures of substances, essentially or completely solvent and water-free liquid mixtures (100% systems), essentially or completely solvent- and water-free solids Powder or substantially or completely solvent-free powder suspensions (Powder slurries). Furthermore can the dual-cure mixtures one-component systems in which the Binder and the crosslinking agents are present side by side, or Two- or multi-component systems in which the binders and the crosslinking agents separated until shortly before application be present.

methodical shows the preparation of the substance mixtures to be used according to the invention no special features on, but is done by mixing and Homogenizing the above-described ingredients using conventional and known mixing methods and devices such as stirred tanks, Agitator mills, extruders, Kneader, Ultraturrax, in-line dissolver, static mixer, micromixer, Sprocket dispersers, pressure relief nozzles and / or Microfluidizer preferably excluding actinic radiation. The selection the for a given individual case optimal method is mainly aimed according to the physical state and the three-dimensional shape, which should have the substance mixture. For example, if a thermoplastic A mixture of substances in the preferred form of a film or a laminate in particular, the extrusion comes through a slot die for the production the mixture and its shape into consideration.

in the Framework of the method according to the invention are the mixtures for the production of hardened materials, in particular thermoset materials, used the most diverse Serve purposes.

Prefers If the mixtures are starting materials for moldings and foils or coatings, adhesives and sealants.

Prefers are the hardened ones Materials around molded parts, foils, coatings, adhesive layers and seals.

Especially the coating materials are used as electrocoats, fillers, antistonechip primers, Solid-color topcoats, waterborne basecoats and / or clearcoats, in particular Clearcoats, for the production of color and / or effect, electrically conductive, magnetically shielding or fluorescent single or multi-layer coatings, in particular color and / or effect multicoat paint systems, used. For the preparation of the multicoat paint systems may be the customary and known wet-on-wet processes and / or Extrusion process and the usual and known paint or film structures are applied.

to Preparation of the cured Materials are used in the inventive method according to the invention Mixtures on usual and known temporary or permanent substrates applied.

Preferably be for the production of films and moldings conventional and known temporary substrates used, such as metal and plastic tapes and films or hollow bodies Metal, glass, plastic, wood or ceramics that are easily removed can be without the films and moldings produced from the mixtures damaged become.

Become the mixtures for used the production of coatings, adhesives and seals, permanent substrates are used, such as bodies of locomotion, in particular motor vehicle bodies, and parts thereof, buildings indoors and outdoors and parts thereof, doors, windows, Furniture, Hollow glassware, Coils, containers, packaging, small parts, optical, mechanical and electrotechnical components and components for white goods. The with the aid of the method according to the invention produced films and moldings can also be used as permanent Serve substrates.

methodical has the application of to be used in the process according to the invention Mixtures no particularities on, but can by all usual and known, for the respective substance mixture suitable application methods, such as e.g. Extrude, electrocoating, spraying, spraying, inclusive Powder spraying, Doctoring, brushing, pouring, Diving, trickling or rolling done. Preferably, extrusion and spray application methods applied. In the application, it is recommended, under exclusion from actinic radiation to work, to premature networking to avoid the substance mixtures.

In a preferred embodiment the method according to the invention the mixtures are in the form of films, especially in the shape of planar laminates comprising at least one film a mixture of substances and optionally at least one carrier film, preferably made of a thermoplastic material used.

In a particularly preferred embodiment the method according to the invention The films or laminates are processed shaping before curing.

The shaping processing is preferably carried out by deep drawing and / or by injection molding with thermoplastic materials ( "Injection Molding ") or reactive precursors of plastics ("Reaction Injection Molding") in conventional and known injection molding machines. This results in curable, shaped films or laminates on appropriately shaped plastic substrates.

Include the curable ones Films or laminates at least one thermoplastic carrier film For example, the films or laminates are preferably so with the substrates or their precursors connected, that the carrier foils the UV radiation sources are averted.

To Their application, the mixtures in the above-described Way hardened.

The resulting hardened Materials, in particular the resulting films, molded parts, Coatings, adhesive layers and seals are ideal for the Coating, bonding, sealing, wrapping and packaging of bodies of means of locomotion, in particular motor vehicle bodies, and parts thereof, indoor and outdoor structures and parts thereof, doors, Windows, furniture, Hollow glassware, Coils, containers, packaging, small parts, such as nuts, screws, Rims or hubcaps, optical components, mechanical components, electrotechnical components, such as winding goods (coils, stators, rotors), as well as components for white Goods, such as radiators, appliances, refrigerator covers or Washing-machine casings.

The inventive method offers very special advantages when it comes to the production of clearcoats is used.

at the clearcoats are usually the outermost ones Layers of multi-layer coatings or films or laminates, which essentially determine the overall visual impression (appearance) and the substrates and / or the color and / or effect layers of multi-layer coatings or films or laminates before mechanical and chemical damage and damage protected by radiation. That's why shortcomings in hardness, scratch resistance and chemical resistance also arise and stability across from Yellowing in the clearcoat particularly noticeable. So but have the inventive method produced clearcoats only a slight yellowing on. They are highly scratch-resistant and show very little after scratching low gloss losses. In particular, the loss of gloss is in the car wash simulation test to Amtec / Kistler very low. At the same time they have a high Hardness and a particularly high chemical resistance. Last but not least they have excellent substrate adhesion and intercoat adhesion, especially when exposed to a jet of steam on.

Production Example 1

The production a radically curable or crosslinkable urethane acrylate

It was a urethane acrylate from the following structural components prepared by hydrogenated bisphenol-A in 2-hydroxyethyl acrylate at 60 ° C with stirring was coarsely dispersed. To this suspension were added the isocyanates, Hydroquinone monomethyl ether, 1,6-di-tert-butyl para-cresol and methyl ethyl ketone given. After the addition of dibutyltin dilaurate warmed the approach. At internal temperature of 75 ° C was stirred for several hours until the NCO value of the reaction mixture practically did not change any more. The optionally present after the reaction still free isocyanate groups were reacted by adding a small amount of methanol.

Structural components:

• 104.214 g of hydrogenated bisphenol-A (corresponding to 0.87 equivalents Hydroxyl groups);
• 147.422 g (corresponding to 0.77 equivalents of isocyanate groups) Basonate ^® HI 100 from BASF AG = Company commercial isocyanurate of hexamethylene diisocyanate with an NCO content of 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 = Company commercially available biuret of hexamethylene diisocyanate with an NCO content of 22-23% (DIN EN ISO 11909);
• 124.994 g (corresponding to 0.51 equivalents of isocyanate groups) Vestanat ^® T1890 Degussa = commercial isocyanurate of isophorone diisocyanate having an NCO content of 11.7 to 12.3% (DIN EN ISO 11909);
• 131.378 g of 2-hydroxyethyl acrylate (corresponding to 1.13 equivalents 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 2,2 ethylenisch ungesättigte Doppelbindungen pro Molekül;
• – einen Doppelbindungsgehalt von 1,74 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 resulting urethane acrylate (radically crosslinkable component) had the following characteristics:

• - An average of 2.2 ethylenically unsaturated double bonds per molecule;
• A double bond content of 1.74 double bonds per 1000 g of urethane acrylate solids;
• On average 2.2 branch points per molecule;
• 25% by weight of cyclic structural elements, based on the solids content of the urethane acrylate.

Production Example 2

The production a curable with UV radiation clearcoat

In a suitable stirred vessel were 100.00 parts by weight of the above-described organic solution of Urethanacrylats of Preparation Example 1 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), 2.0 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 (commercially available photoinitiator from BASF Aktiengesellschaft based on 2, 4,6-trimethylbenzoyl-diphenyl-phosphine oxide), 2.40 parts by weight of Irgacure ^® 184 (commercial photoinitiator from Ciba Specialty Chemicals, based on 1-hydroxycyclohexyl phenyl ketone) and 0.2 parts by weight of Byk ^® 306 (commercially available Additive from Byk Chemie based on a polyether-modified polydimethylsiloxane) with constant stirring at room temperature in 3-butoxy-2-propanol dissolved 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.

Production Example 3

The production of a coated, thermoplastic carrier film

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"). Of the Basecoat was made with the aid of a box wiper of width 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 layer (first Basecoat layer) was 100 μm. The wet first basecoat layer was left on for 3 minutes Conditions ventilated and subsequently up to a residual content of volatile Substances of 4% by weight, based on the first basecoat film, dried. The resulting conditioned first basecoat layer a layer thickness of about 20 microns was on with chill rolls a surface temperature <30 ° C is set.

• – 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.

The same basecoat was applied to the conditioned and tempered first basecoat film 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 inflow the film), a constant temperature of 21 ± 1 ° C and a constant relative Humidity 65 ± 5% carried out. The layer thickness of the resulting wet basecoat layer (second Basecoat layer) was 50 ± 2 μm. The second Basecoat was under these conditions during 3 Bleeding off minutes and then until to a residual content of volatile Substances of 4 wt .-%, based on the second basecoat layer, dried. The air temperature was 90 ° C, the humidity at 10g / min and the air speeds at 10 m / s. The resulting conditioned second basecoat layer of a layer thickness of about 10 microns was with chill rolls set to a surface temperature <30 ° C.

On the conditioned and tempered second basecoat film, the UV-curable clearcoat according to was used with the aid of a doctor blade width of 37 cm. Preparation Example 2 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 of 65 ± 5%. The layer thickness of the resulting wet clearcoat layer was 120 μm. It was flashed off under the conditions mentioned for 6 minutes and then dried to a residual volatile content of 2.5% by weight, based on the clearcoat film. The air temperature in the oven was 119 ° C for all drying stages. The resulting dried, but not yet fully cured coating of a layer thickness of 60 .mu.m was set with cooling rollers to a surface temperature <30 ° C and with the in the DE 103 35 620 A1 , Example 1, protective film made of polypropylene (commercial product GH-X 527 Bishop + Klein, Lengerich) coated.

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

Examples 1 to 3

The production of plastic moldings

Plastic moldings were produced according to the following general instructions:
The multilayer film acc. Preparation Example 3 was preformed. Subsequently, the transparent, not yet fully cured coating was completely crosslinked after removal of the protective film with UV radiation. As a positive mold, a cube was used. The resulting preformed part was placed in a mold. The tool was closed and the cube was back-injected with a liquid plastic material.

For the irradiation a UV emitter from Arccure was used (undoped mercury tube). This Spotlight was designed so that no UV radiation directly on the plastic moldings met, but only indirectly reflected Radiation in two bundled Strips. For both reflected stripes could have different reflectors which reflected the entire UV spectrum ("wide"), the long-wavelength Proportion of the UV spectrum stronger on the plastic moldings reflected ("A + B") or the shortwave portion of the UV spectrum stronger reflected on the sample ("C"). In the examples 1 and 3 to 6, in the direction of passage of the plastic moldings through the UV exposure system seen, the reflectors arrangement: 1. "wide" and 2. "C", selected. In Example 2, the reflector arrangement: 1. "A + B" and 2. "A + B" was selected.

The Plastic moldings were irradiated in an oxygen depleted carbon dioxide atmosphere.

• a) Abstand zwischen UV-Strahlenquelle und Oberfläche der Klarlackschicht;
• b) Sauerstoffgehalt der Atmosphäre oberhalb der Klarlackschicht;
• c), d) gemessen mit einem PowerPuck^® der Firma EIT;
• e) Restglanz nach der Belastung im Waschstraßensimulationstest nach Amtec/Kistler mit Reinigung (Abwischen mit Waschbenzin);
• f) Dampfstrahltest;

The table provides an overview of the shortest distances between the UV radiation source and the surface of the clearcoat film of the plastic moldings, the oxygen content of the atmosphere over the clearcoat film, the spectral distribution with the associated dose and performance and the scratch resistance and adhesion of the resulting clearcoats of the plastic moldings. Table: The curing of the clearcoat films with UV radiation and important properties of the clearcoats

• a) distance between the UV radiation source and the surface of the clearcoat film;
• b) oxygen content of the atmosphere above the clearcoat layer;
• c), d) as measured by a EIT Power Puck ^® of the company;
• e) residual gloss after exposure in the car wash simulation test according to Amtec / Kistler with cleaning (wiping with benzine);
• f) steam jet test;

at the car wash simulation test became a lab wash the company Amtec Kistler (see T. Klimmasch, T. Engbert, Technology Days, Cologne, DFO, Report Volume 32, pages 59 to 66, 1997). The stress was determined by measuring the residual gloss of the sample after the wash line simulation test and subsequent wiping with a wipe impregnated with benzine certainly. Residual gloss levels greater than 80% were achieved.

For the steam jet test gem. became known in the art test instructions for the Daimler-Benz steam jet test in each case a St. Andrew's cross in the clearcoats of Examples 1 scratched to 6. The scratches were made with a jet of water sprayed (Device the company Walter type LTA2; Pressure: 67 bar; Water temperature: 60 ° C; distance Nozzle tip / test specimen: 10 cm; Load duration: 60 seconds; Device setting: F 1).

Of the Degree of flaking and sub-migration was assessed visually. In all cases the result was i. O. (okay).

The results of the table substantiate that the clearcoats of the plastic moldings of Examples 1 to 6 have a very good intercoat adhesion and a high scratch resistance, in particular under Pra xis conditions.

Otherwise were the clearcoats of the plastic moldings of the examples 1 to 6 brilliant and had a very high gloss (20 °) according to DIN 67530 on. They were tough, flexible, chemical resistant and free of disturbing Yellowing.

Claims (24)

Process for producing hardened materials from compositions curable with actinic radiation (mixtures of substances) by irradiation with UV radiation, characterized in that UV radiation of the following spectral distribution and dose is used: wavelength λ = 400 to 320 nm; Dose = 500 to 2,500 mJ / cm ² ; Wavelength λ = 320 to 290 nm; Dose = 700 to 3,000 mJ / cm ² ; Wavelength λ = 290 to 180 nm; Dose = 100 to 500 mJ / cm ² . A method according to claim 1, characterized in that one uses UV radiation of the following spectral distribution and dose: - wavelength λ = 400 to 320 nm; Dose = 750 to 2,000 mJ / cm ² ; Wavelength λ = 320 to 290 nm; Dose = 1,000 to 2,200 mJ / cm ² ; Wavelength λ = 290 to 180 nm; Dose = 200 to 450 mJ / cm ² . A method according to claim 1 or 2, characterized in that one uses UV radiation of the following spectral distribution and power: - wavelength λ = 400 to 320 nm; Power = 100 to 600 mW / cm ² ; Wavelength λ = 320 to 290 nm; Power = 100 to 600 mW / cm ² ; Wavelength λ = 290 to 180 nm; Power = 20 to 120 mW / cm ² . A method according to claim 3, characterized in that one uses UV radiation of the following spectral distribution and power: - wavelength λ = 400 to 320 nm; Power = 120 to 550 mW / cm ² ; Wavelength λ = 320 to 290 nm; Power = 140 to 550 mW / cm ² ; Wavelength λ = 290 to 180 nm; Power = 30 to 100 mW / cm ² . Method according to one of claims 1 to 4, characterized that during irradiation the distance of the source of UV radiation to the surface of the mixture is 20 to 250 mm. Method according to claim 5, characterized in that that the distance is 40 to 100 mm. Method according to one of claims 1 to 6, characterized that during irradiation the oxygen content of the atmosphere at the surface the substance mixture is depleted. Method according to claim 7, characterized in that the oxygen content of the atmosphere is <18% by volume. Method according to one of claims 1 to 8, characterized that the mixtures in addition are physically and / or thermally curable. Method according to one of claims 1 to 9, characterized that the mixtures as films or as components of laminates available. Method according to one of claims 1 to 10, characterized in that the mixtures after their curing has a storage modulus E 'in the rubber elastic range of at least 10 ^7.5 Pa and a loss factor tanδ at 20 ° C of not more than 0.10, wherein the storage module E 'and the loss factor tanδ have been measured by dynamic mechanical thermal analysis (DMTA) on free films with a layer thickness of 40 ± 10 μm, Method according to one of claims 1 to 11, characterized that the mixtures have a content of activatable with UV radiation Have bonds of 0.5 to 6 meq / g of solids. A method according to claim 12, characterized in that the content of activating with UV radiation baren bonds at 1 to 4 meq / g solids. Method according to claim 12 or 13, characterized that with UV radiation activatable bonds carbon-carbon double bonds are. Method according to one of claims 1 to 14, characterized that the mixtures at least one radically crosslinkable component contain that (i) one or more oligo- and / or one or contains several polyurethane (meth) acrylates and (ii) in the statistical Means more than one olefinically unsaturated double bond per molecule, (Iii) a number average molecular weight of 1,000 to 10,000 daltons, (Iv) a double bond content of 1.0 to 5.0 double bonds per 1,000 g radically crosslinkable component, (v) in the statistical Mean per molecule> 1 branch point, (Vi) From 5 to 50% by weight, based in each case on the weight of the component, cyclic structural elements and (vii) at least one aliphatic Structural element with at least 6 carbon atoms in the chain having, wherein the radically crosslinkable component carbamate and / or Biuret and / or allophanate and / or urea and / or amide groups contains. Method according to one of claims 1 to 15, characterized that the substance mixtures coating materials, adhesives, sealants and starting products for Moldings and films are. Method according to claim 16, characterized in that that the hardened Materials coatings, adhesives, gaskets, moldings and Slides are. Method according to claim 16, characterized in that that the coating materials electrocoating, filler or Rockfall protection primers, solid-color topcoats, basecoats or clearcoats which are used for the production of coatings. Method according to claim 17 or 18, characterized that the coatings are electrodeposition coatings, surfacer coatings, Antistonechip primers, solid-color topcoats, basecoats or clearcoats are. Method according to claim 18 or 19, characterized that the coatings color and / or effect multi-layer coatings or films or laminates. Process for producing hardened materials according to one the claims 1 to 19, characterized in that the mixtures on permanent or temporary Substrates applied and irradiated with UV radiation. Method according to claim 21, characterized that the substrates of metal, plastic, glass, wood, textile, leather, Natural and artificial stone, concrete, cement or composites of these materials consist. Method according to claim 21 or 22, characterized that the moldings and films are removed from the temporary substrates. Method according to one of claims 21 to 23, characterized that the permanent substrates are bodies of locomotion and parts thereof, interior and exterior structures and parts thereof, doors, Windows, furniture, Hollow glassware, Coils, containers, packaging, small parts, optical, mechanical and electrical components and components for white goods.