Stock material or miscellaneous articles – Composite – Of polyamidoester
Reexamination Certificate
1998-02-17
2001-03-20
Nakarani, D. S. (Department: 1773)
Stock material or miscellaneous articles
Composite
Of polyamidoester
C156S330900, C156S331400, C156S331700, C428S423700, C428S425100, C428S428000
Reexamination Certificate
active
06203915
ABSTRACT:
The present invention relates to a laminate, to a process for its preparation and to its use.
BACKGROUND OF THE INVENTION
EP-A-374 551 discloses coated substrates suitable for producing add-on parts for automobile bodies. The coated substrates described consist of metal panels coated with at least one paint film or of composite materials whose surface layer consists of the painted metal parts. P 4424290.9 discloses substrates coated with two or more layers. These substrates are formed and processed with or without the aid of further materials. In this way it is possible to produce add-on parts for vehicle bodies.
According to this prior art, therefore, a metal panel is coated with a filler onto which a paint is then applied. The metal panel is subsequently cut and formed. In some cases, the form is punched directly from the panel.
A problem with is technique is that the painted metal must be bent, in some cases by up to 180°. It is therefore necessary for the coating material applied to be sufficiently flexible that at the broken edge no cracks are formed which might be a source of corrosion.
The flexibly formulated coating materials, however, are so soft that their surface can readily be damaged by sharp objects.
The object of the present invention was, accordingly, to provide a laminate which no longer has the disadvantages set out above.
SUMMARY OF THE INVENTION
This object is achieved by a laminate consisting of
a) a plastic film,
b) an adhesion-promoting layer based on polyurethane
consisting of one or more polyester- or polyetherdiols having a molecular weight of from 500 to 2500, preferably from 800 to 1000,
c) if desired, a further plastic film,
d) if desired, a layer of a coating material,
e) if desired, a filler layer, and
f) a layer of support material, preferably of plastic, wood or metal.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Suitable materials for the plastic films a) and c) of the invention are preferably thermoplastics. It is possible, for example, to employ films of polyolefin, polyamide, polyurethane, polyester, polyacrylate, polycarbonate or a mixture of these polymeric substances. Particular preference is given in accordance with the invention to polyurethanes and polyesters.
A suitable polyurethane film is preferably thermoplastic polyurethane, stabilized against ultraviolet radiation, based on diisocyanates, diols as chain extenders, polytetrahydrofuran or linear polyesterdiols.
Thermoplastic polyurethanes of this kind can be prepared, for example, by the belt method or extruder method, by reaction of
a) organic, preferably aliphatic, cycloaliphatic or, in particular, aromatic diisocyanates,
b) polyhydroxy compounds having molecular weights of from 500 to 3000 and
c) chain extenders having molecular weights of from 60 to 400,
d) if desired in the presence of catalysts,
e) auxiliaries and/or additives.
The starting materials (a) to (c), catalysts (d), auxiliaries and additives (e) which can be used for this purpose are described in more detail below:
a) Suitable organic diisocyanates (a) are preferably aliphatic, cycloaliphatic and, in particular, aromatic diisocyanates. Specific examples that may be mentioned are: aliphatic diisocyanates, such as hexamethylene 1,6-diisocyanate, methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate or mixtures of at least 2 of these C
6
-alkylene diisocyanates, pentamethylene 1,5-diisocyanate and butylene 1,4-diisocyanate, cycloaliphatic diisocyanates, such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and -2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4′-, 2,4′-and 2,2′-dicyclohexylmethyl diisocyanate and the corresponding isomer mixtures, and preferably aromatic diisocyanates, such as 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6-tolylene diisocyanate, 4,4′-, 2,4′- and 2,2′-diphenylmethane diisocyanate, mixtures of 2,4′-and 4,4′-diphenylmethane diisocyanate, urethane-modified, liquid 1,2-(4,4′- and/or 2,4′-diisocyanatodiphenyl)ethane and 1,5-naphthylene diisocyanate. It is preferred to use hexamethylene 1,6-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate isomer mixtures with a 4,4′-diphenylmethane diisocyanate content of greater than 96% by weight, and especially 4,4′-diphenylmethane diisocyanate.
b) Suitable polyhydroxy compounds (b) of relatively high molecular mass, having molecular weights of from 500 to 3000, are preferably polyetherols and polyesterols. Also suitable, however, are hydroxyl-containing polymers, for example polyacetals, such as polyoxymethylenes and especially water-insoluble formals, examples being polybutanediol formal and polyhexanediol formal, and aliphatic polycarbonates, especially those of diphenyl carbonate and 1,6-hexanediol, prepared by transesterification, having the abovementioned molecular weights. The polyhydroxy compounds must be at least predominantly linear, i.e. of difunctional composition for the purposes of the isocyanate reaction. The polyhydroxy compounds specified can be employed as individual components or in the form of mixtures.
Suitable polyetherols can be prepared by known methods, for example by anionic polymerization with alkali metal hydroxides, such as sodium or potassium hydroxide, or alkali metal alcoholates, such as sodium methylate, sodium or potassium ethylate or potassium isopropylate as catalysts or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate, etc., or bleaching earth as catalysts, of one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical and, if desired, a starter molecule containing 2 reactive hydrogen atoms in bonded form.
Examples of alkylene oxides that may be mentioned are: ethylene oxide, 1,2-propylene oxide, tetrahydrofuran, 1,2- and 2,3-butylene oxide. Employed preferably are ethylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide. The alkylene oxides can be used individually, alternately in succession or as a mixtures. Examples of suitable starter molecules are: water, amino alcohols, such as N-alkyl-dialkanolamines, an example being N-methyl-diethanolamine, and diols, for example alkanediols or dialkylene glycols having 2 to 12 C atoms, preferably 2 to 6 C atoms, such as ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. It is also possible if desired to employ mixtures of starter molecules. Further suitable polyetherols are the hydroxyl-containing polymerization products of tetrahydrofuran (polyoxytetramethylene glycols).
Preference is given to the use of polyetherols of 1,2-propylene oxide and ethylene oxide in which more than 50%, preferably from 60 to 80% of the OH groups are primary hydroxyl groups and in which at least some of the ethylene oxide is arranged as a terminal block, and especially polyoxytetramethylene glycols.
Such polyetherols can be obtained by polymerizing first the 1,2-propylene oxide and then, subsequently, the ethylene oxide onto the starter molecule, or first of all copolymerizing all of the 1,2-propylene oxide in a mixture with some of the ethylene oxide, and subsequently polymerizing on the remainder of the ethylene oxide, or, in a stepwise procedure, polymerizing first some of the ethylene oxide, then all of the 1,2-propylene oxide and then the remainder of the ethylene oxide onto the starter molecule.
The essentially linear polyetherols possess molecular weights of from 500 to 3000, preferably from 500 to 2500 and, in particular, from 800 to 1000. They can be employed both individually and in the form of mixtures with one another.
Suitable polyesterols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 8 carbon atoms, and polyhydric alcohols. Examples of suitable dicarboxylic acids are: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, suberic acid, azelaic acid, sebacic acid and, preferably, adipic acid, and aromatic dicarboxylic a
Kiriazis Leonidas
Prissok Frank
BASF Coatings AG
Nakarani D. S.
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