WO2001038427A1 - Lacquered moulded parts consisting of synthetic material, method for their production and the use thereof - Google Patents
Lacquered moulded parts consisting of synthetic material, method for their production and the use thereof Download PDFInfo
- Publication number
- WO2001038427A1 WO2001038427A1 PCT/EP2000/010652 EP0010652W WO0138427A1 WO 2001038427 A1 WO2001038427 A1 WO 2001038427A1 EP 0010652 W EP0010652 W EP 0010652W WO 0138427 A1 WO0138427 A1 WO 0138427A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- plastic
- graft
- lacquer
- rubber
- copolymer
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
Definitions
- the present invention relates to new painted plastic molded parts.
- the present invention also relates to a new process for its production.
- the present invention relates to the use of the new painted plastic molded parts for the production of motor vehicle bodies, in particular automobile bodies.
- Plastic moldings in particular large-area plastic moldings, are becoming increasingly important in the manufacture of motor vehicle bodies, in particular automobile bodies, because of their ease of manufacture, their comparatively low weight and their outstanding profile of application properties, which can be specifically adapted to the particular intended use. It is necessary to further improve the hardness and scratch resistance of large plastic outer parts.
- PPE / PA polyphenylene ether and polyamide
- PBT / PC polybutylene terephthalate and polycarbonate
- the plastic parts are coated with a scratch-resistant clear lacquer.
- a scratch-resistant clear lacquer For process engineering, ecological and economic reasons, it is essential that the clear lacquers used crosslink as quickly as possible at room temperature and if possible do not cause any emissions of organic compounds.
- UV clearcoats as described, for example, in German patent DE-C-197 09 467. These UV clear coats are so-called 100% systems, which contain no organic solvents, harden within seconds when irradiated with actinic radiation and deliver highly scratch-resistant coatings.
- German patent DE-C-197 09 467 shows that the known UV clearcoats can also be used to coat plastics. However, it is not specified which plastics are suitable.
- the coating of Teflon and polypropylene described in Examples 1 to 4 and lines 40 to 44 of page 3 of the German patent only serves to produce free films for measuring the storage module E 'and the loss factor tan ⁇ with the dynamic mechanical thermal Analysis (DMTA), since the films from the known hardened UV clearcoats do not adhere to these polymers, but can be removed easily and without damage.
- DMTA dynamic mechanical thermal Analysis
- the plastic moldings made of PBT / PC which have so far been used mainly by motor vehicle manufacturers, have the serious disadvantage that their toughness, in particular at low temperatures, and their elongation at break are drastically reduced by painting. This can go so far that the lacquered plastic molded parts are no longer suitable for outdoor applications in which they are subjected to severe mechanical stress, for example due to stone chipping. This disadvantageous effect also occurs when using the UV clearcoats known from German patent DE-C-197 09 467.
- the object of the present invention is to find new coated plastic molded parts which no longer have the disadvantages of the prior art, but which can be given a highly scratch-resistant coating without their other application properties which are essential for external use on motor vehicle bodies being affected become.
- the new painted plastic molded parts should also have an excellent overall visual impression, excellent weather resistance, moisture resistance and chemical resistance as well as excellent adhesion between plastics and paints.
- the clear coat should not cause a shift in the color of colored plastic molded parts.
- (al2) at least one graft pad made of at least one copolymer with a glass transition temperature above 30 ° C.
- the memory module E 'and the loss factor tan ⁇ with the Dynamic mechanical thermal analysis (DMTA) on free homogeneous films with a layer thickness of 40 ⁇ 10 ⁇ m were measured.
- plastic molded part according to the invention.
- (al2) at least one graft pad made of at least one copolymer with a glass transition temperature above 30 ° C.
- a paint which, in the cured state, has a storage module E 'in the rubber-elastic range of at least 10 7 ' 6 Pa and a loss factor tan ⁇ at 20 ° C of a maximum of 0.1, whereby the storage module E 'and the loss factor tan ⁇ were measured with dynamic mechanical thermal analysis (DMTA) on free homogeneous films with a layer thickness of 40 ⁇ 10 ⁇ m.
- DMTA dynamic mechanical thermal analysis
- the plastic molding according to the invention contains at least one plastic layer (A) as an essential component of the invention.
- the plastic molding according to the invention can be a laminate that is made up of at least two layers of different material composition. It is essential here that at least one plastic layer (A) forms the outermost layer of the laminate, so that it is in direct contact with the paint.
- the molded plastic part according to the invention but can also consist only of a plastic layer (A). Which variant is chosen depends on the technical requirements associated with the respective purposes.
- the plastic molding according to the invention is of any external shape. So it can have the shape of a flat or curved plate, which can have perforations and / or surface structures. It can also have a compact three-dimensional shape. Examples of such shapes are hubcaps, fenders, sills, bumpers, bonnets, trunk lids, wind deflectors, spoilers, housings for screens or telephones, household appliances or furniture.
- the plastic layer (A) to be used according to the invention contains or consists of at least one graft copolymer (a1). Which variant is chosen depends on the technical requirements of the respective purpose.
- the graft copolymer (al) to be used according to the invention consists of at least one, in particular one, rubber-elastic polymer (al l) with a glass transition temperature of below 10 ° C., preferably below 0 ° C., preferably -20 ° C. and in particular -25 ° C. graft.
- suitable polymers (A1) are natural rubber, synthetic rubber based on conjugated dienes, optionally i. V. m. further copolymers or elastomers based on Ci to C alkyl esters of acrylic acid, which may contain further comonomers.
- Polybutadiene cf. German patent specifications DE-A-14 20 775 or DE-A-14 95 089 or the copolymers are preferred as the graft base (A1) from polybutadiene and styrene (cf. British Patent GB-A-649 166). OH
- graft bases (al 1) are constructed from, in each case based on the graft base (al l),
- (11 al) 70 to 99.9 wt .-%, in particular 99 wt .-% of at least one Ci to C 8 -alkyl acrylate, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, in particular n-butyl acrylate;
- al l2 0 to 30% by weight, in particular 0 to 20% by weight, of at least one further monofunctional olefinically unsaturated monomer which can be copolymerized therewith, such as butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate and / or vinyl methyl ether; and
- al l3 0.1 to 5% by weight, in particular 1 to 4% by weight, of at least one polyfunctional, in particular bifunctional or trifunctional, olefinically unsaturated monomers which bring about crosslinking and which are copolymerizable therewith, which is not in the 1.3 Position is conjugated, such as divinylbenzene, maleic acid diallyl ester, fumaric acid diallyl ester,
- the polymers (al 1) or the graft bases (al 1) in the graft copolymers (al) are preferably in an amount of, based on the Graft copolymer (al), 40 to 80 wt .-%, preferably 45 to 75 wt .-% and in particular 50 to 70 wt .-%.
- the graft copolymer (a1) contains at least one graft pad (a1) with a glass transition temperature above 30 ° C.
- the outermost graft layer (al2) preferably has a glass transition temperature above 30 ° C., a polymer formed from the monomers of the graft layer (al2) having a glass transition temperature of more than 80 ° C.
- Particularly suitable grafting layers result if styrene or alpha-methylstyrene or mixtures of styrene and acrylonitrile, alpha-methylstyrene and acrylonitrile, styrene, acrylonitrile and methyl methacrylate or styrene and maleic anhydride are used as monomers (al21 or al22).
- Particularly suitable graft layers (al2) contain, in each case based on the graft base (al2), 50 to 95% by weight, in particular 60 to 80% by weight, of at least one monomer (al21) and 5 to 50% by weight , in particular 20 to 40 wt .-%, of at least one monomer (al22).
- the graft layers (a1) can be obtained by copolymerizing the monomers (a121) and (a122) described above.
- the graft copolymer (al) contains a graft base (al l), which is made up of polybutadiene polymers, one speaks of acrylonitrile-butadiene-styrene graft polymers or rubbers, which are also referred to by the experts as ABS.
- the graft copolymerization has no peculiarities, but takes place according to the customary and known methods of graft copolymerization in solution, suspension or, preferably, emulsion, as described, for example, in German patent DE-A-31 49 358.
- the graft base or soft phase (al l) has an average particle diameter (d 0 value of the integral mass distribution) of 0.08 ⁇ m.
- the d 5 o value is set in the range from 0.2 to 0.5 ⁇ m by enlarging the particles, for example by agglomeration or when the emulsion is obtained by means of the seed latex method.
- the polymerizing monomers (a 121) and (a 122) are at least partially linked to the already polymerized rubber (al 1), the linkage probably occurring at the double bonds contained in the rubber as graft centers.
- the grafting can also be carried out in several stages by first grafting on part of the monomers (al21) and (al22) forming the graft shell or overlays (al2) and then the rest.
- the graft copolymer (al) contains a graft base (all)
- the acrylic acid is made up of elastomers on the basis of Ci to C 8 alkyl esters, one speaks of acrylate-styrene-acrylonitrile graft copolymers or rubbers, which experts also refer to as ASA for short.
- Their manufacture is known per se and is described, for example, in German patents DE-A-28 26 925, DE-A-31 49 358, DE-A-43 14 118 or DE-A-196 51 350.
- the graft copolymers (A1) can be prepared, for example, by the method described in German patent DE-C-12 60 135.
- the graft cover or cover (al2) can be constructed in one or two stages.
- the first stage In the case of a two-stage construction of the graft shell (al2), the first stage generally makes up 20 to 70% by weight, preferably 25 to 50% by weight, in each case based on (al2). Only monofunctional vinyl aromatic monomers (al21) are preferably used for their preparation.
- the second stage of the graft shell generally makes up 30 to 80% by weight, in particular 50 to 75% by weight, in each case based on (al2).
- mixtures of the monomers (al21) and (al22) are preferably used in a weight ratio (al21): (al22) of 90:10 to 60:40, in particular 80:20 to 70:30.
- the conditions of the graft copolymerization are preferably chosen so that particle sizes of 50 to 700 nm (d 50 value of the integral mass distribution) result. Appropriate measures are known and z. B. described in German Patent DE-A-28 26 925.
- a coarse-particle rubber dispersion can be produced directly using the seed latex process.
- a mixture of at least two graft copolymers (al 1) with different particle sizes is often used. This can be achieved by the particles of the rubber z. B. be enlarged by agglomeration, so that the latex bimodal (d 5 o values of the integral mass distribution: 50 to 180 nm and 200 to 700 nm) is established.
- the chemical structure of the two graft copolymers (al2) is preferably the same, although the shell of the coarse-particle graft copolymer can also be constructed in several stages, in particular in two stages.
- the graft pad is preferably contained in the ABS or ASA (al) to be used according to the invention in an amount of 20 to 60% by weight, preferably 30 to 50% by weight, based on (al).
- the content of ASA or ABS (al) in the plastic layer (A) can vary widely.
- the plastic layer (A) consists of ASA or ABS (al).
- the plastic layer (A) or the mixture of substances (A) that builds up the plastic layer (A) contains further constituents.
- the lower limit of the ASA or ABS (al) content then results from the level of toughness, which is still sufficient for a given purpose. The person skilled in the art can therefore determine the content on the basis of his specialist knowledge, if necessary with the aid of simple preliminary tests.
- the proportion of ASA or ABS (al) in the plastic layer (A) or in the material mixture (A) of which it consists, based on their total amount, is preferably 1 to 99% by weight, preferably 3 to 90% by weight .-%, particularly preferably 5 to 80 wt .-% and in particular 10 to 70 wt .-%.
- Suitable further constituents are halogen-free thermoplastic copolymers (a2). If they are used, their share in the plastic layer (A) can vary widely.
- the upper limit of the proportion results from the level of toughness of the plastic layer (A), which is still sufficient for a given purpose. The upper limit can therefore easily be determined by the person skilled in the art on the basis of his specialist knowledge, possibly with the aid of simple preliminary tests.
- the proportion of (a2) to (A), based on (A), is preferably 5 to 90% by weight, preferably 10 to 85% by weight, particularly preferably 15 to 80% by weight and in particular 20 to 70% by weight.
- Such copolymers (a2) often arise as by-products in the preparation of the graft copolymers (al), in particular when comparatively large amounts of monomers (al21) and (al22) are grafted onto comparatively small amounts of graft bases (al l). They can also be produced in a targeted manner by radical copolymerization, in particular by emulsion, suspension, solution or bulk polymerization. They have viscosity numbers in the range from 40 to 160, which corresponds to mass average molecular weights of 40,000,000,000.
- Aromatic polycarbonates (a3) are further examples of highly suitable further constituents.
- the proportion of polycarbonates (a3) in the plastic layer (A) can also vary widely and depends on the requirements of the particular application. The person skilled in the art can therefore determine the advantageous portion in a simple manner on the basis of his specialist knowledge, if necessary with the aid of simple preliminary tests.
- the plastic layer (A) or the mixture of substances (A) from which it is composed preferably contains, based on (A), 10 to 80% by weight, preferably 15 to 75% by weight, particularly preferably 20 to 70% by weight. -% and in particular 25 to 65 wt .-% of at least one polycarbonate (a3).
- Suitable polycarbonates (a3) are those based on diphenols of the general formula I,
- X represents a single bond, an alkylene group with 1 to 3 carbon atoms, an alkylidene group with 2 or 3 carbon atoms, a cycloalkylidene group, -S- or -SO 2 -.
- diphenols I 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1 Bis (4-hydroxyphenyl) cyclohexane, of which bisphenol A and l, l-bis (4-hydroxyphenyl) cyclohexane are particularly advantageous and are therefore used with particular preference.
- suitable diphenols are hydroquinone or resorcinol.
- polycarbonates (a3) Both homopolycarbonates and copolycarbonates are suitable as polycarbonates (a3).
- the polycarbonates (a3) can be branched in a known manner. This is preferably achieved by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of compounds having at least three phenolic hydroxyl groups.
- the particularly suitable polycarbonates (a3) have relative viscosities of 1.10 to 1.50, in particular 1.25 to 1.40, which corresponds to a weight average molecular weight of 10,000 to 200,000, preferably 20,000 to 80,000.
- the production of the polycarbonates (a3) has no special features in terms of method, but instead takes place by reacting the diphenols with phosgene according to the phase interface process or the process in a homogeneous phase, the so-called pyridine process.
- the molecular weight to be set in each case is achieved in a known manner by a corresponding amount of customary and known chain terminators.
- chain terminators are phenol or p-tert-butylphenol or long-chain alkylphenols according to German patent DE-A-28 42 005 such as 4- (1,3-tetramethylbutyl) phenol, monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents according to German patent DE-A-35 06 472 such as p-nonylphenol, 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-
- the polycarbonates (a3) described above are preferably halogen-free, polycarbonates (a3) which have ppm contents of saponifiable chlorine, which originate from the production of the polycarbonates (a3) with phosgene by the phase interface process, being regarded as halogen-free by their nature.
- the plastic layer (A) or the mixture of substances (A) from which it is composed can contain additives, as are usually used in the plastics described above, in effective amounts.
- Suitable additives are dyes, pigments, antistatic agents, antioxidants, lubricants and lubricants, mold release agents, flame retardants or stabilizers to improve thermal stability, light stability, resistance to hydrolysis or chemical resistance.
- the production of the plastic layer (A) to be used according to the invention has no special features in terms of method, but instead is carried out by producing the mixture of substances (A) to be used according to the invention in a customarily unknown manner, for example by mixing the above-described constituents in solution or in bulk in a kneader or a Extruder, after which - if appropriate after removal of the solvent - the resulting mixture of substances (A) is subjected to shaping processes as are customary and known in the field of thermoplastics, in particular extrusion combined with calendering, injection molding, film blowing and / or laminating.
- the further component of the plastic molding according to the invention which is essential to the invention is at least one coating (B) located on the plastic layer (A).
- the coating (B) to be used according to the invention can be produced from a coating which, in the hardened state, has a storage module E 'in the rubber-elastic range of at least 10 7 ' 6 Pa, in particular at least 10 8 ' 0 Pa, and a loss factor tan ⁇ at 20 ° C of a maximum of 0.1, in particular a maximum of 0.06, the memory module E ' and the loss factor tan ⁇ were measured with the Dynamic Mechanical Thermal Analysis (DMTA) on free homogeneous films with a layer thickness of 40 + 10 ⁇ m.
- DMTA Dynamic Mechanical Thermal Analysis
- the loss factor tan ⁇ is defined as the quotient of the loss module E "and the memory module E '.
- Dynamic mechanical thermal analysis is a generally known measurement method for determining the viscoelastic properties of coatings and is described, for example, in Murayama, T., Dynamic Mechanical Analysis of Polymeric Material, Esevier, New York, 1978 and Loren W. Hill, Journal of Coatings Technology, Vol. 64. No. 808, May 1992, pages 31 to 33.
- the measurements can be carried out, for example, using the MK II, MK III or MK IV devices from Rheometrics Scientific.
- the storage module E 'and the loss factor tan ⁇ are measured on homogeneous free films.
- the free films are produced in a known manner by applying and curing the coating agent on substrates to which the coating agent does not adhere.
- Glass, Teflon and in particular polypropylene may be mentioned as examples of suitable substrates.
- Polypropylene has the advantage of good availability and is therefore normally used as a carrier material.
- the layer thickness of the free films used for the measurement is generally 40 + 10 ⁇ m.
- the special selection of the lacquers based on the value of the storage module in the rubber-elastic range and the loss factor at 20 ° C. of the hardened lacquers enables the provision of lacquers in a simple manner (B) with the desired property profile of good scratch resistance with good polishability, chemical and moisture resistance and weather resistance, since both parameters can be determined by simple DMTA measurements. Furthermore, the resulting coatings (B) have a high gloss and an acid and base resistance, which is comparable to the corresponding values of conventional, thermally hardened coatings.
- lacquers (B) with a high scratch resistance also result in lacquers which have only a medium or even a small plastic fraction at the test temperature, but which have a high to very high storage modulus in the rubber-elastic range.
- the coatings (B), which were produced from the coatings selected according to the criteria described above, have excellent adhesion to the plastic layer (A) of the plastic molding according to the invention.
- Coating agents with the corresponding above Viscoelastic properties are preferred by means of actinic radiation, in particular electromagnetic radiation such as near infrared light (NIR), visible light, UV radiation or X-rays and / or corpuscular radiation such as electron-curable lacquers.
- actinic radiation in particular electromagnetic radiation such as near infrared light (NIR), visible light, UV radiation or X-rays and / or corpuscular radiation such as electron-curable lacquers.
- NIR near infrared light
- UV radiation visible light
- UV radiation or X-rays / or corpuscular radiation
- electron-curable lacquers electron-curable lacquers.
- the lacquers curable with UV radiation are advantageous here and are used with particular preference according to the invention.
- varnishes based on organically modified ceramic materials which are sold, for example, under the ORMOCER® brand, are also suitable for the production of the varnishes (B).
- These radiation-curable paints usually contain at least one, preferably more, radiation-curable binders, in particular based on olefinically unsaturated prepolymers and / or olefinically unsaturated oligomers, optionally one or more reactive diluents, optionally one or more photoinitiators and optionally conventional paint additives.
- Radiation-curable lacquers are preferably used whose viscosity at 23 ° C. is less than 100 s run-down time in the DIN 4 cup, particularly preferably less than 80 s run-out time in the DIN 4 cup.
- the binders used in these radiation-curable lacquers are, for example, (meth) acrylic-functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and the corresponding methacrylates. It is preferred to use binders which are free from aromatic structural units.
- the use of epoxy acrylates leads to hard, scratch-resistant coatings, but they generally show weather resistance in need of improvement.
- Urethane (meth) acrylates and / or polyester (meth) acrylates are therefore preferably used, particularly preferably aliphatic urethane acrylates.
- essentially silicone-free, particularly preferably silicone-free, binders are preferably used, since the resulting lacquers have an improved ability to overcoat compared to silicone-containing lacquers.
- the polymers or oligomers used as binders usually have a number average molecular weight of 500 to 50,000, preferably 1,000 to 5,000.
- Polymers and / or oligomers which have at least 2, particularly preferably 3 to 6, double bonds per molecule are preferably used in the coatings.
- the binders used preferably also have a double bond equivalent weight of 400 to 2,000, particularly preferably of 500 to 900, on.
- the binders preferably have a viscosity of 250 to 11,000 mPa.s at 23 ° C.
- Polyester (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. In addition, there is the possibility of using hydroxyalkyl esters of (meth) acrylic acid as an alcohol component directly in the construction of the polyesters. However, the polyester (meth) acrylates are preferably prepared by acrylating polyester. For example, polyesters containing hydroxyl groups can first be built up, which are then reacted with acrylic or methacrylic acid. It is also possible first to build up polyesters containing carboxyl groups, which are then reacted with a hydroxyalkyl ester of acrylic or methacrylic acid.
- Unreacted (meth) acrylic acid can be obtained by washing, distilling, or preferably by reacting with an equivalent amount of a mono- or diepoxide compound using suitable catalysts, e.g. Triphenylphosphine, are removed from the reaction mixture.
- suitable catalysts e.g. Triphenylphosphine
- Polyether (meth) acrylates are also known in principle to the person skilled in the art. They can be produced by various methods. For example, polyethers containing hydroxyl groups, which are esterified with acrylic acid and / or methacrylic acid, can be reacted by reacting di- and / or polyhydric alcohols with different amounts of ethylene oxide and / or propylene oxide using well-known methods (cf., for example, Houben-Weyl, Volume XIV , 2, Macromolecular Substances II, (1963)) can be obtained. Polymerization products of tetrahydrofuran or butylene oxide can also be used.
- the polyether (meth) acrylates and the polyester (meth) acrylates can be made more flexible, for example, by corresponding OH-functional prepolymers or oligomers (polyether or polyester base) with longer-chain, aliphatic dicarboxylic acids, in particular aliphatic dicarboxylic acids with at least 6 ° C. -Atoms, such as adipic acid, sebacic acid, dodecanedioic acid and / or dimer fatty acids, are reacted.
- This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
- epoxy (meth) acrylates are also well known to the person skilled in the art and therefore do not need to be explained in more detail. They are usually produced by adding acrylic acid to epoxy resins, for example to epoxy resins based on bisphenol A or other commercially available epoxy resins.
- the epoxy (meth) acrylates can be made more flexible, for example, by reacting corresponding epoxy-functional prepolymers or oligomers with longer-chain, aliphatic dicarboxylic acids, in particular aliphatic dicarboxylic acids with at least 6 carbon atoms, such as adipic acid, sebacic acid, dodecanedioic acid and / or dimer fatty acids , This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
- Urethane (meth) acrylates are also well known to the person skilled in the art and therefore do not need to be explained in more detail. They can be obtained by reacting a di- or polyisocyanate with a chain extender from the group of the diols / polyols and / or diamines / polyamines and / or dithiols / polythiols and / or alkanolamines and then reacting the remaining free isocyanate groups with at least one Hydroxyalkyl (meth) acrylate or hydroxyalkyl esters of other ethylenically unsaturated carboxylic acids.
- chain extender di- or polyisocyanate and hydroxyalkyl ester
- the equivalent ratio of the NCO groups to the reactive groups of the chain extender is between 3: 1 and 1: 2, preferably 2: 1, and
- the hydroxyl groups of the hydroxyalkyl esters of the olefinically unsaturated carboxylic acids are present in a stoichiometric amount in relation to the free isocyanate groups of the prepolymer composed of isocyanate and chain extender.
- the polyurethane acrylates by first reacting some of the isocyanate groups of a di- or polyisocyanate with at least one hydroxyalkyl ester and then reacting the remaining isocyanate groups with a chain extender.
- the amounts of chain extender, isocyanate and hydroxyalkyl ester are chosen so that the equivalent ratio of the NCO groups to the reactive groups of the chain extender is between 3: 1 and 1: 2, preferably 2: 1, and the equivalent ratio of the remaining NCO Groups to the hydroxyl groups of the hydroxyalkyl ester is 1: 1.
- all intermediate forms of these two processes are also possible.
- part of the isocyanate groups of a diisocyanate can first be reacted with a diol, then another part of the isocyanate groups can be reacted with the hydroxyalkyl ester and then the remaining isocyanate groups can be reacted with a diamine.
- These various manufacturing processes for polyurethane acrylates are known (cf., for example, European patent specification EP-A-0 204 161) and therefore do not require a more detailed description.
- the urethane (meth) acrylates can be made more flexible, for example, by reacting corresponding isocyanate-functional prepolymers or oligomers with longer-chain, aliphatic diols and / or diamines, in particular aliphatic diols and / or diamines with at least 6 carbon atoms.
- This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
- the binder is used in the lacquers to be used according to the invention preferably in an amount of 5 to 90% by weight, particularly preferably 20 to 70% by weight, in each case based on the total weight of the lacquer in the case of clear lacquers or on the weight of the Lacquers without pigments and fillers are used in the case of pigmented systems.
- the lacquers may also contain one or more reactive thinners.
- the reactive diluents can be olefinically unsaturated compounds.
- the reactive diluents can be mono-, di- or polyunsaturated. They usually serve to influence the viscosity and the paint properties, such as the crosslinking density.
- the reactive diluent (s) are preferably present in the lacquers in an amount of 0 to 70% by weight, particularly preferably 15 to 65% by weight, in each case based on the total weight of the lacquer in the case of clear lacquers or on the weight of the Lacquers without pigments and fillers are used in the case of pigmented systems.
- Reactive diluents include, for example, (meth) acrylic acid and its esters, maleic acid and its esters or half esters, vinyl acetate, vinyl ether, vinyl ureas and others. used. Examples include alkylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate,
- the two acrylate groups can be separated by a polyoxybutylene structure . It is also possible to use 1,12-dodecyl diacrylate and the reaction product of 2 moles of acrylic acid with one mole of a dimer fatty alcohol, which generally has 36 carbon atoms. Mixtures of the monomers mentioned are also suitable.
- Preferred reactive diluents are mono- and / or diaciylates, such as e.g. Isobomylacrylate, hexanediol diacrylate, tripropylene glycol diacrylate, Laromer® 8887 from BASF AG and Actilane® 423 from Akcros Chemicals Ltd., Great Britain. Isobomylacrylate, hexanediol diacrylate and tripropylene glycol diacrylate are particularly preferably used.
- the paints optionally contain, preferably in amounts of 0 to 10% by weight, preferably 2 to 6% by weight, based on the weight of the paint without pigments and fillers, customary photoinitiators used in radiation-curable coating compositions, for example benzophenones, benzoins or Benzoin ether, preferably benzophenone.
- customary photoinitiators used in radiation-curable coating compositions for example benzophenones, benzoins or Benzoin ether, preferably benzophenone.
- Products which are commercially available under the brands Irgacure® 184, Irgacure® 1800 and Irgacure® 500 from Ciba Geigy, Grenocure® MBF from Rahn and Lucirin® TPO from BASF AG can also be used.
- the paints may also contain customary paint additives, for example light stabilizers (e.g. HALS compounds, benzotriazoles,
- Oxalanilide, etc. slip additives, polymerization inhibitors, matting agents, defoamers, leveling agents and film-binding aids, for example cellulose Derivatives, or other additives commonly used in paints.
- paint additives are usually used in an amount of up to 50% by weight, preferably up to 45% by weight, based on the weight of the paint, without pigments and without fillers. Further examples of suitable paint additives are described in the textbook "Paint Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.
- the lacquers are used in particular as clear lacquers, so that they usually contain no or only transparent fillers and no opaque pigments. However, it can also be used in the form of pigmented lacquers.
- the paints contain 2 to 40% by weight. based on the total weight of the paint, one or more pigments. Furthermore, in this case the lacquers can still contain 1 to 20% by weight, based on the total weight of the lacquer, of one or more fillers.
- Page volume concentration Page 563 »Thioindigo Pigments «; Page 567 »Titanium dioxide pigments «; and pages 250 ff., "Fillers"; directed.
- lacquers to be used according to the invention have no special features in terms of method, but instead are carried out in a customary and known manner by mixing the constituents described above in solution or in the melt in suitable mixing units such as dissolvers, stirred kettles, extruders or stirrer mills, suitable measures being taken, For example, working with lighting with visible light of a wavelength of over 550 nm or with the exclusion of light in order to avoid premature crosslinking of the paints.
- suitable mixing units such as dissolvers, stirred kettles, extruders or stirrer mills
- the paint described above is preferably applied in a wet film thickness such that after curing in the finished paint (B), in particular clear coat (B), a dry film thickness of 10 to 250, preferably 15 to 200 , particularly preferably 20 to 150 and in particular 20 to 100 ⁇ m results.
- the application of the varnish can be done by all usual application methods, e.g. Spraying, knife coating, painting, pouring, dipping or rolling.
- Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot air hot spraying.
- the application can be carried out at temperatures of max. 70 to 80 ° Celsius are carried out so that suitable application viscosities are achieved without the change in or damage to the lacquer and its overspray, which may have to be reprocessed, occurring under the briefly acting thermal load.
- hot spraying can be designed in such a way that the paint is heated only very briefly in or shortly before the spray nozzle.
- the spray booth used for the application can be operated, for example, with a circulation that can be tempered, if necessary, which is equipped with a suitable absorption medium for the overspray, e.g. B. the paint itself is operated.
- a suitable absorption medium for the overspray e.g. B. the paint itself is operated.
- the application is preferably carried out when illuminated with visible light of a wavelength of over 550 nm or with exclusion of light. hereby a material change or damage to the paint and the overspray are avoided.
- the lacquer layer resulting on the plastic layer (A) is hardened with actinic radiation.
- the hardening can take place after a certain rest period. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min.
- the rest period is used, for example, for the course and degassing of the paint layers or for the evaporation of volatile components such as solvents.
- the rest period can be supported and / or shortened by the use of elevated temperatures up to 90 ° C and or by a reduced humidity ⁇ 10g water / kg air, in particular ⁇ 5g / kg air, provided that no damage or changes to the paint layers occur, for example evaporation of the reactive diluents or premature complete crosslinking.
- the usual and known radiation sources and optical auxiliary measures are used for curing with actinic radiation.
- suitable radiation sources are high-pressure or low-pressure mercury vapor lamps, which may be doped with lead in order to open a radiation window up to 405 nm, or electron beam sources.
- Their arrangement is known in principle and can be adapted to the conditions of the plastic molding according to the invention and the process parameters.
- the areas not directly accessible to radiation such as cavities, folds and other undercuts due to construction, with point, small area or all-round emitters combined with an automatic movement device for irradiating cavities or edges (partially) can be cured become.
- Curing with actinic radiation is preferably carried out under an inert gas atmosphere.
- plastic moldings according to the invention produced in the procedure according to the invention described above can be used for a variety of applications due to their particular advantages.
- the manufacture of motor vehicle bodies and commodities, including housings for electrotechnical and electronic components and furniture, may be mentioned as examples.
- the plastic moldings according to the invention have a better visual impression and a longer service life than conventional painted plastic moldings, which makes them economically particularly attractive for the user.
- a UV-curable lacquer based on the total amount of lacquer, was made from 54% by weight of a urethane acrylate, prepared by reacting the isocyanurate of hexamethylene diisocyanate with 2-hydroxyethyl acrylate, 43% by weight of 1.6%.
- Hexanediol diacrylate and 3% by weight of the photoinitiator Irgacure® 500 from the company Ciba Specialty Chemicals is made by vigorous stirring using a dissolver.
- the viscoelastic characteristics of homogeneously cured films of the lacquer were determined by DMTA measurements, as described in the German patent DE-C-197 09 467.
- the storage module E ' was 10 8 ' 3 Pa, the loss factor tan ⁇ at 20 ° C was 0.005.
- Example 3 A commercial ASA was used for Example 3 (Luran® S 778T from BASF Aktiengesellschaft).
- Example 4 A commercial ABS (Terluran® GP-22 from BASF Aktiengesellschaft) was used for Example 4.
- plastic moldings according to the invention were produced which had the customary and known standardized dimensions which were required for the measurements indicated in Table 1 and which had a coating of 50 ⁇ m thick on one side, produced from the coating according to the preparation example 1 were coated by UV radiation with a dose of 1,500 mJ / cm 2 .
- Examples 1 and 2 were repeated for comparative experiments VI and V2, and examples 3 and 4 were repeated for comparative experiments V5 and V6, except that the plastic moldings were not coated with the coating.
- Table 1 the results of the measurements according to the examples are compared with the results of the measurements according to comparative experiments VI in pairs (1 / V1, 2 / V2, 3 / V5 and 4 / V6).
- the comparison shows that the mechanical properties of the blends were only slightly affected, if at all, by the coating (1 / V1 and INT).
- the level of the mechanical properties of ASA and ABS was reduced by the paint, but this was still within an acceptable range.
- Example 1 was repeated for comparative experiment V3, except that a commercially available blend of polybutylene terephthalate (PBT) and PC was used instead of the blend of ABS and PC.
- PBT polybutylene terephthalate
- comparative experiment V4 comparative experiment VI was repeated, except that instead of the blend of ABS and PC, a commercially available blend of PBT and PC was used.
- Table 1 shows the results of the measurements according to comparative tests V3 and V4. The results show that the blend of PBT and PC was more severely damaged in its mechanical properties by the coating.
- V3 3.04 2.5 3.03 12.8 4.3 5.1 V4 33,, 0033 1133,, 44 3.03 72.5 78.5 54.5
- plastic molded parts according to the invention were produced from Luran® S KR 2864C, which had the customary and known standardized dimensions which were required for the tests described below and which had a 50 ⁇ m coating on one side, produced from the coating according to the preparation example 1 were coated by UV radiation with a dose of 1,500 mJ / cm 2 .
- Test duration 668; Degree of bladder lh after exercise: amount
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Graft Or Block Polymers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00975955A EP1235873A1 (en) | 1999-11-24 | 2000-10-30 | Lacquered moulded parts consisting of synthetic material, method for their production and the use thereof |
CA002392100A CA2392100A1 (en) | 1999-11-24 | 2000-10-30 | Lacquered moulded parts consisting of synthetic material, method for their production and the use thereof |
AU13896/01A AU1389601A (en) | 1999-11-24 | 2000-10-30 | Lacquered moulded parts consisting of synthetic material, method for their production and the use thereof |
BR0015791-0A BR0015791A (en) | 1999-11-24 | 2000-10-30 | Lacquered synthetic molded parts, processes for producing them and using them |
MXPA02004533A MXPA02004533A (en) | 1999-11-24 | 2000-10-30 | Lacquered moulded parts consisting of synthetic material, method for their production and the use thereof. |
JP2001540187A JP2003514971A (en) | 1999-11-24 | 2000-10-30 | Coated plastic molded article, its production method and its use |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19956483A DE19956483A1 (en) | 1999-11-24 | 1999-11-24 | Lacquered molded plastic parts, process for their production and their use |
DE19956483.3 | 1999-11-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001038427A1 true WO2001038427A1 (en) | 2001-05-31 |
Family
ID=7930142
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/010652 WO2001038427A1 (en) | 1999-11-24 | 2000-10-30 | Lacquered moulded parts consisting of synthetic material, method for their production and the use thereof |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1235873A1 (en) |
JP (1) | JP2003514971A (en) |
AU (1) | AU1389601A (en) |
BR (1) | BR0015791A (en) |
CA (1) | CA2392100A1 (en) |
DE (1) | DE19956483A1 (en) |
MX (1) | MXPA02004533A (en) |
WO (1) | WO2001038427A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003061849A1 (en) * | 2002-01-24 | 2003-07-31 | Basf Coatings Ag | Hardened materials, method for the production thereof, and use thereof |
WO2003101631A1 (en) * | 2002-06-01 | 2003-12-11 | Basf Coatings Ag | Scratch-resistant coated substrates and a method for the production thereof |
US7399793B2 (en) | 2003-10-31 | 2008-07-15 | Basf Corporation | Coating composition curable with ultraviolet radiation |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10233521A1 (en) * | 2002-07-23 | 2004-02-05 | Basf Ag | Radiation-curable coating systems with low-temperature elastic underlayer |
EP1844917A3 (en) | 2006-03-24 | 2008-12-03 | Entex Rust & Mitschke GmbH | Method for processing products which must be degassed |
FR2910877B1 (en) | 2006-12-28 | 2009-09-25 | Eurocopter France | IMPROVEMENT TO ROTORS OF GIRAVIONS EQUIPPED WITH INTERPAL SHOCK ABSORBERS |
EP2289687A1 (en) | 2007-05-16 | 2011-03-02 | Entex Rust & Mitschke GmbH | Method for machining products to be degassed |
DE102011112081A1 (en) | 2011-05-11 | 2015-08-20 | Entex Rust & Mitschke Gmbh | Process for processing elastics |
WO2014056553A1 (en) | 2012-10-11 | 2014-04-17 | Entex Gmbh Rust & Mitschke Gmbh | Extruder for processing plastics which are suitable for adhesion |
JP6084062B2 (en) * | 2013-02-01 | 2017-02-22 | アート・アンド・テック株式会社 | Compound colored sheet |
WO2014206958A1 (en) * | 2013-06-27 | 2014-12-31 | Bayer Materialscience Ag | Metallizable, scratch-resistant and solvent-resistant film |
DE102015001167A1 (en) | 2015-02-02 | 2016-08-04 | Entex Rust & Mitschke Gmbh | Degassing during the extrusion of plastics |
DE102017001093A1 (en) | 2016-04-07 | 2017-10-26 | Entex Rust & Mitschke Gmbh | Degassing during the extrusion of plastics with sintered metal filter discs |
DE102015008406A1 (en) | 2015-07-02 | 2017-04-13 | Entex Rust & Mitschke Gmbh | Process for processing products in the extruder |
DE102016002143A1 (en) | 2016-02-25 | 2017-08-31 | Entex Rust & Mitschke Gmbh | Filling module in planetary roller extruder design |
DE102017006638A1 (en) | 2017-07-13 | 2019-01-17 | Entex Rust & Mitschke Gmbh | Filling module in planetary roller extruder design |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1946820A1 (en) * | 1968-09-17 | 1970-05-06 | Ici Ltd | Process for the production of molded and coated polymer articles |
US5703139A (en) * | 1994-09-27 | 1997-12-30 | Hanwha Chemical Corporation | Photo-curable resin composition and product coated therewith |
DE19709465A1 (en) * | 1997-03-07 | 1998-09-17 | Basf Coatings Ag | Process for the production of scratch-resistant coatings, in particular for the production of multi-layer coatings |
DE19709467C1 (en) * | 1997-03-07 | 1998-10-15 | Basf Coatings Ag | Coating compositions and processes for producing multicoat paint systems |
-
1999
- 1999-11-24 DE DE19956483A patent/DE19956483A1/en not_active Withdrawn
-
2000
- 2000-10-30 CA CA002392100A patent/CA2392100A1/en not_active Abandoned
- 2000-10-30 BR BR0015791-0A patent/BR0015791A/en not_active IP Right Cessation
- 2000-10-30 JP JP2001540187A patent/JP2003514971A/en active Pending
- 2000-10-30 WO PCT/EP2000/010652 patent/WO2001038427A1/en not_active Application Discontinuation
- 2000-10-30 AU AU13896/01A patent/AU1389601A/en not_active Abandoned
- 2000-10-30 MX MXPA02004533A patent/MXPA02004533A/en unknown
- 2000-10-30 EP EP00975955A patent/EP1235873A1/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1946820A1 (en) * | 1968-09-17 | 1970-05-06 | Ici Ltd | Process for the production of molded and coated polymer articles |
US5703139A (en) * | 1994-09-27 | 1997-12-30 | Hanwha Chemical Corporation | Photo-curable resin composition and product coated therewith |
DE19709465A1 (en) * | 1997-03-07 | 1998-09-17 | Basf Coatings Ag | Process for the production of scratch-resistant coatings, in particular for the production of multi-layer coatings |
DE19709467C1 (en) * | 1997-03-07 | 1998-10-15 | Basf Coatings Ag | Coating compositions and processes for producing multicoat paint systems |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003061849A1 (en) * | 2002-01-24 | 2003-07-31 | Basf Coatings Ag | Hardened materials, method for the production thereof, and use thereof |
WO2003101631A1 (en) * | 2002-06-01 | 2003-12-11 | Basf Coatings Ag | Scratch-resistant coated substrates and a method for the production thereof |
US7399793B2 (en) | 2003-10-31 | 2008-07-15 | Basf Corporation | Coating composition curable with ultraviolet radiation |
Also Published As
Publication number | Publication date |
---|---|
CA2392100A1 (en) | 2001-05-31 |
MXPA02004533A (en) | 2002-09-02 |
BR0015791A (en) | 2002-07-16 |
AU1389601A (en) | 2001-06-04 |
EP1235873A1 (en) | 2002-09-04 |
DE19956483A1 (en) | 2001-06-28 |
JP2003514971A (en) | 2003-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE68921130T2 (en) | Process for producing a composite structure from thermoplastic and fiber mats (SMC). | |
WO2001038427A1 (en) | Lacquered moulded parts consisting of synthetic material, method for their production and the use thereof | |
DE3915459C2 (en) | ||
EP1015131B1 (en) | Method for producing multi-layer paints | |
DE69004312T2 (en) | Peeling-resistant coatings and application processes therefor. | |
DE60128038T2 (en) | Curable resin and coating composition | |
DE68926669T2 (en) | COMPOSITE MATERIAL FROM THERMOPLASTIC POLYOLEFIN | |
DE69630219T2 (en) | MOLDED PLASTIC ITEMS WITH SCRATCH-RESISTANT ORGANIC HARD COATING LAYER AND FOG-FREE ORGANIC HARD COATING LAYER, METHOD FOR THE PRODUCTION THEREOF, AND COATING MATERIALS THEREFOR | |
DE68915158T2 (en) | In-mold thermosetting coating compositions. | |
DE60225144T2 (en) | RAY-HARDENED POWDER LACK COMPOSITIONS | |
EP0628610B1 (en) | Scratch-resistant anti-soiling and anti-graffiti coating for mouldings | |
DE19633959B4 (en) | Shaped body with an ornamental film and a method for its production | |
EP0270831A2 (en) | Polymerisable solvent-free hot melt having a very low or no monomer content, process for its preparation and use | |
DE3739791C2 (en) | Metallic painting | |
DE19938759A1 (en) | Coating material and its use for the production of highly scratch-resistant multi-layer clear coats | |
DE4128897A1 (en) | COATING PROCESS | |
DE602004008257T2 (en) | FAST CRYSTALLIZING POLYESTER COMPOSITIONS | |
EP3013912B1 (en) | Metallizable, scratch-resistant and solvent-resistant film | |
DE3887828T2 (en) | Reactive coatings. | |
DE60220518T2 (en) | Acrylic urethane coating composition | |
DE10140145A1 (en) | Coating materials curable thermally and with actinic radiation and their use | |
EP1121387A1 (en) | Film and the use thereof for coating shaped parts | |
DE4116312A1 (en) | POLYOLEFINIC COATING RESIN COMPOSITIONS | |
EP0659829B1 (en) | Weather-resistant sheet and articles coated therewith | |
DE60126552T2 (en) | Method for two-way coating |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2000975955 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2002/004533 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2392100 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 2001 540187 Kind code of ref document: A Format of ref document f/p: F |
|
WWP | Wipo information: published in national office |
Ref document number: 2000975955 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2000975955 Country of ref document: EP |