EP1404767A1 - Physikalisch oder thermisch und/oder mit aktinischer strahlung härtbare, lösemittelhaltige gemische, verfahren zu ihrer herstellung und ihrer verwendung - Google Patents
Physikalisch oder thermisch und/oder mit aktinischer strahlung härtbare, lösemittelhaltige gemische, verfahren zu ihrer herstellung und ihrer verwendungInfo
- Publication number
- EP1404767A1 EP1404767A1 EP02743235A EP02743235A EP1404767A1 EP 1404767 A1 EP1404767 A1 EP 1404767A1 EP 02743235 A EP02743235 A EP 02743235A EP 02743235 A EP02743235 A EP 02743235A EP 1404767 A1 EP1404767 A1 EP 1404767A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solvent
- organic solvents
- curable
- boiling organic
- boiling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
Definitions
- the present invention relates to new, solvent-containing mixtures which are curable physically or thermally and / or with actinic radiation.
- the present invention relates to a new process for the production of physically or thermally and / or actinic radiation-curable, solvent-containing mixtures.
- the present invention relates to the use of the new, solvent-containing mixtures curable physically or thermally and / or with actinic radiation as coating materials, adhesives and sealants.
- Solvent-containing mixtures curable physically or thermally and / or with actinic radiation have long been known.
- the known solvent-containing mixtures can be pigmented or unpigmented. They are used as pigmented and unpigmented coating materials, adhesives and sealants, but in particular as pigmented and unpigmented coating materials.
- the pigmented and unpigmented coating materials can be used for a wide variety of purposes. For example, they can be used for the painting of motor vehicle bodies and parts thereof, of motor vehicles inside and outside, buildings inside and outside, doors, windows and furniture as well as for the industrial painting of the coating of coils, containers, packaging, small parts, serve electrical components and white goods. Particularly high demands are made of the pigmented and unpigmented coating materials when they are used for the initial painting of motor vehicle bodies and parts thereof (OEM) and for the repair painting of motor vehicles indoors and outdoors. The highest demands are placed on the first painting and refinishing of luxury cars. In general, automotive coatings are considered to be the top products in the coatings industry (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Automobillacke", pages 49 and 50).
- the pigmented coating materials can be used to produce filler coatings and stone chip protection primers, solid-color top coats and basecoats.
- the unpigmented coating materials are used to produce clear coats.
- This multi-layer coating is referred to here and below as a color and / or effect multi-layer coating.
- the clear coats form the outermost layer, they protect the coats underneath and shape the overall appearance (appearance) of the multi-coat paint and / or effect coating by deepening the visual effect of the base coat.
- the clearcoats are responsible for optical, mechanical and chemical properties, such as gloss, distinctness of image (DOI), hardness, scratch resistance, weather stability, chemical stability and etch resistance.
- the non-pigmented coating materials which can provide clear coats of this application-related property profile, must have a very good flow and a very low tendency to run during application and curing, so that clear coat layers free of surface defects occur. These must not tend to form stoves, pinholes, cracks and orange peel structures during hardening.
- the object of the present invention is to provide new, solvent-containing, pigmented and unpigmented mixtures which are curable physically or thermally and / or with actinic radiation and which no longer have the disadvantages of the prior art, but which are outstanding as pigmented and unpigmented coating materials, Let adhesives and sealants, especially pigmented and unpigmented coating materials, or use them to make them.
- the pigmented coating materials are said to be outstandingly suitable as fillers, solid-color topcoats or basecoats for the production of color and / or effect-giving multi-layer lacquers which include filler lacquers or stone chip protection primers and solid color lacquers or filler lacquers or stone chip protection primers, basecoats and clearcoats.
- the unpigmented coating materials are said to be particularly suitable as clear lacquers for producing color and / or effect multi-layer coatings.
- the clearcoats should be able to be used for the production of these color and / or effect multicoat paint systems by integrated wet-on-wet processes, in which at least one dried, but not fully cured basecoat film is covered with a clearcoat film, after which the two layers together be hardened.
- the resulting filler coatings or stone chip protection primers, solid-color top coats, basecoats and clear coats, but especially clear coats, should have an excellent, trouble-free surface without stoves, pinholes, cracks and orange peel structures.
- the clear coats should have a higher gloss, a higher distinctness of image (DOI) and better appearance than the clear coats of the prior art.
- the clear coats should be hard, scratch-resistant. activity, weather stability, chemical stability and etch resistance correspond to the clearcoats of the prior art.
- HSP Hildebrand solubility parameter ⁇
- HBI hydrogen bonding index
- HSP Hildebrand solubility parameter ⁇
- HBI hydrogen bonding index
- HSP Hildebrand solubility parameter ⁇
- HBI hydrogen bonding index
- the coating materials, adhesives and sealants according to the invention which contained the aromatic-free solvent mixtures to be used according to the invention, provided coatings, adhesive layers and seals with very good to excellent performance properties.
- the coatings according to the invention had excellent, trouble-free surfaces without stoves, pinholes, cracks and orange peel structures.
- the clearcoats of the invention surprisingly showed a higher gloss, a higher degree of differentiation (DOL) and better appearance than the clearcoats of the prior art.
- the clearcoats of the invention corresponded in their hardness, scratch resistance, weathering stability, chemical stability and etch resistance in full to the clearcoats of the prior art.
- free of aromatics means that the aromatic-free solvent mixtures to be used according to the invention have an aromatic solvent content of less than 1.0% by weight, preferably less than 0.1% by weight and in particular below the gas chromatographic detection limit.
- “completely free from aromatic solvents” means that the mixtures according to the invention, based on their total amount, contain less than 1.0% by weight and in particular less than 0.1% by weight of aromatic solvents.
- the aromatic solvent content is below the gas chromatographic detection limit.
- “Essentially free from aromatic solvents” means that the mixtures according to the invention may contain a certain aromatic solvent content which, based on its total amount, is> 1.0% by weight, but this content does not apply to those to be used according to the invention aromatic-free organic solvents medium goes back, but to aromatic solvents which are forcibly "carried in” by the other constituents of the mixtures according to the invention, such as binders or crosslinking agents.
- actinic radiation means electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation and X-rays, in particular UV radiation, and corpuscular radiation, such as electron beams.
- NIR near infrared
- UV radiation visible light
- UV radiation ultraviolet radiation
- corpuscular radiation such as electron beams.
- Hildebrand solubility parameter ⁇ [(cal / cm 3 ) 172 ] is defined in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Solubility parameters", pages 361 to 365.
- HBI Hydrogen Bonding Index
- “Physical hardening” is understood to mean the hardening of a layer of the mixture according to the invention by filming, the connection within the coating via loop formation of the polymer molecules of the binders (for the term cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Binders”, pages 73 and 74), or the filming takes place via the coalescence of binder particles (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Här- tion «, pages 274 and 275). No crosslinking agents are usually necessary for this. If necessary, the physical hardening can be supported by atmospheric oxygen, heat or by exposure to actinic radiation.
- the mixtures according to the invention can furthermore be thermally curable. Here, they can be self-cross-linking or cross-linking.
- self-crosslinking denotes the property of a binder to undergo crosslinking reactions with itself.
- the prerequisite for this is that both types of complementary reactive functional groups which are necessary for thermal crosslinking or reactive functional groups are already present in the binders of the mixtures according to the invention
- mixtures according to the invention are designated as crosslinking in which one type of the complementary reactive functional groups is present in the binder and the other type is present in a hardener or crosslinking agent Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Hardening", pages 274 to 276, especially page 275, below.
- the mixtures according to the invention can be curable with actinic radiation.
- curing takes place via groups which contain bonds which can be activated with actinic radiation.
- the mixtures according to the invention can be curable thermally and with actinic radiation. If thermal and curing with actinic radiation are used together in a mixture according to the invention, one also speaks of “dual cure” and “dual cure mixture”.
- the mixtures according to the invention can be one-component (1K) systems.
- One-component (1K) systems are understood as thermal or thermal and with actinic radiation-curing mixtures according to the invention in which the binder and the crosslinking agent are present side by side.
- the prerequisite for this is that the two components only crosslink with one another at higher temperatures and / or when irradiated with actinic radiation.
- the mixtures according to the invention can be two- or multi-component systems.
- the binders and the crosslinking agents are stored separately from one another until shortly before the mixtures according to the invention are used.
- the aromatic-free solvent mixture to be used according to the invention contains at least one, in particular one, low-boiling organic solvent (A) and at least one organic solvent (B), in particular two organic solvents (B), selected from the group consisting of high-boiling and medium-boiling organic solvents , or it consists of these organic solvents.
- the aromatic-free solvent mixtures to be used according to the invention can thus low-boiling solvents (A) and high-boiling solvents (B),
- Low-boiling solvents (A) and medium-boiling solvents (B) are preferably used.
- Low-boiling organic solvents (A) are understood here and below to mean solvents which boil below 120 ° C. under normal pressure.
- Medium boiling organic solvents (B) are understood here and below to mean solvents which boil between 120 ° C. and 190 ° C. at normal pressure.
- High-boiling organic solvents (B) are understood here and below to mean solvents which boil above 190 ° C. under normal pressure.
- the aromatic-free solvent mixture can also contain minor amounts of non-aromatic organic solvents that differ from the organic solvents (A) and (B).
- a minor proportion is ⁇ 50, preferably ⁇ 40, particularly preferably ⁇ 30, very particularly preferably ⁇ 20 and in particular ⁇ 10% by weight, in each case based on the total amount of the aromatic-free solvent mixture, to understand. This proportion only varies the dissolving properties of the aromatic-free solvent mixture, but does not decisively influence them.
- the aromatic-free solvent mixture consists of the organic solvents (A) and (B).
- the weight ratio of organic solvents (A) to organic solvents (B) can vary very widely and depends in particular on the solubility properties of the other constituents of the mixtures according to the invention and the evaporation behavior necessary for problem-free application and filming.
- the weight ratio (A): (B) is preferably 1:15 to 2: 1, preferably 1:10 to 1.5: 1, particularly preferably 1: 9 to 1.3: 1, very particularly preferably 1: 8 to 1, 2: 1 and in particular 1: 7 to 1, 1: 1.
- HSP Hildebrand solubility parameter ⁇
- HBI hydrogen bonding index
- the low-boiling organic solvents (A) preferably have a Hildebrand solubility parameter ⁇ (HSP) between 10.5 and 12.0 (cal / cm 3 ) 1/2 and a hydrogen bonding index (HBI) between -15 and - 20.
- the medium-boiling and high-boiling organic solvents (B) preferably have a Hildebrand solubility parameter ⁇ (HSP) between 8 and 9.7 (cal / cm 3 ) 1/2 and a hydrogen bonding index (HBI) between 0 and 12 ,
- n-butanol is preferably used.
- glycolic acid butyl ester (GB ester), butyl acetate 98/100%, ethoxypropyl acetate (EPA), ethyl ethoxypropionate (EEP) and methyl amyl ketone (MAK) are preferably used.
- ITA isotridecyl alcohol
- DBE dibasic ester
- BDGA butyl diglycol acetate
- DEOD 2,4-dimethyl-1,5-octanediol
- the rule according to the invention for the selection of the organic solvents (A) and (B) leads to aromatic-free solvent mixtures to be used according to the invention, which not only can completely replace conventional and known aromatic solvents, but also that when substituting the aromatic solvents Improve the profile of properties of the relevant physically, thermally and / or actinic radiation, solvent-containing mixtures and the products produced from them significantly, but are also largely toxicologically and ecologically or completely harmless.
- the content of the aromatic-free solvent mixtures to be used according to the invention in the mixtures according to the invention can vary very widely and depends in particular on the solubility of the other constituents of the mixtures according to the invention, the viscosity required for the Processing, in particular the application, of the mixtures according to the invention is necessary, and the evaporation behavior that is to be set for a specific purpose.
- the aromatic-free solvent mixtures in the mixtures according to the invention are preferably 5 to 95, preferably 6 to 90, particularly preferably 7 to 85, very particularly preferably 8 to 80 and in particular 9 to 75% by weight, in each case based on the mixture according to the invention.
- the mixtures according to the invention can be used extremely widely. They are particularly preferably used as coating materials, adhesives and sealants or for their production.
- the coating materials, adhesives and sealants according to the invention can be curable physically, thermally, with actinic radiation and thermally and with actinic radiation (dual-cure).
- mixtures according to the invention in particular the coating materials, adhesives and sealants according to the invention, can, for example, in addition to the aromatic-free solvent mixtures to be used according to the invention
- the mixtures according to the invention can contain binders and, if appropriate, crosslinking agents and / or additives.
- the binders are oligomeric and polymeric resins. Oligomers are understood to mean resins which contain at least 2 to 15 monomer units in their molecule. In the context of the present invention, polymers are understood to be resins which contain at least 10 recurring monomer units in their molecule. In addition to these terms, reference is made to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, »Oligomere «, page 425.
- Suitable binders are random, alternating and / or block-like linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins. These terms are supplemented by Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition” and “Polyaddifionsharze (polyadducts)", as well as pages 463 and 464, "Polykondensate”, “ Polycondensation ”and“ Polycondensation Resins ”, as well as pages 73 and 74,“ Binder ”.
- binders can generally be used as main binders in the context of the invention.
- Main binders are those binders which have the largest quantitative proportion of the various binders that may be used.
- polyacrylates, polyesters, polyurethanes, polyepoxides and alkyd resins, optionally oil-modified, which may contain hydroxyl groups are suitable. According to the invention, hydroxyl-containing polyacrylates or polyacrylate resins are advantageous and are therefore used with preference.
- the binder can be a polyacrylate resin which can be prepared by (a) 16 to 51% by weight, preferably 16 to 28% by weight, of a hydroxyl-containing ester of acrylic acid or methacrylic acid or a mixture thereof Monomers, (b) 32 to 84% by weight, preferably 32 to 63% by weight, of one of (a) different aliphatic or cycloaliphatic esters of acrylic acid or methacrylic acid with preferably at least 4 carbon atoms in the alcohol radical or a mixture of such monomers, (c) 0 to 2% by weight, preferably 0 to 1% by weight, an ethylenically unsaturated carboxylic acid or a mixture of ethylenically unsaturated carboxylic acids and (d) 0 to 30% by weight, preferably 0 to 20 wt .-%, one of (a), (b) and (c) different ethylenically unsaturated monomer or a mixture of such monomers to form
- the polyacrylate resins used with preference can be prepared in bulk, solution or emulsion by generally known polymerization processes.
- Polymerization processes for the production of polyacrylate resins are generally known and have been described many times (see, for example: Houben Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/1, pages 24 to 255 (1961)).
- the polyacrylate resins used are preferably produced using the solution polymerization process.
- An organic solvent or solvent mixture is usually initially introduced and heated to boiling.
- the monomer mixture to be polymerized and one or more polymerization initiators are then continuously added to this organic solvent or solvent mixture.
- the polymerization takes place at temperatures between 100 and 160 ° C., preferably between 130 and 150 ° C.
- Free radical initiators are preferably used as the polymerization initiators.
- the initiator force and amount are usually chosen so that the supply of radicals is as constant as possible at the polymerization temperature during the feed phase.
- initiators which can be used are: dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; Azodinitriles such as azobisisobutyronitrile or C-C-cleaving initiators such as benzpinacol silyl ether.
- dialkyl peroxides such as di-tert-butyl peroxide or dicumyl peroxide
- Hydroperoxides such as cumene hydroperoxide or tert-butyl hydroperoxide
- Peresters such as tert-butyl perbenzo
- the polymerization conditions (reaction temperature, feed time of the monomer mixture, amount and type of organic solvents and polymerization initiators, possible use of molecular weight regulators, such as mercaptans, thiol glycolic acid esters and hydrogen chloride) are selected so that the polyacrylate resins used, for example, have a number average molecular weight of 1,500 to 10,000, preferably 2,000 to 5,000 (determined by gel permeation chromatography using polystyrene as calibration substance) sen.
- the acid number of the polyacrylate resins used can be adjusted by the person skilled in the art by using appropriate amounts of component (c). The same applies to the setting of the hydroxyl number. It can be controlled via the amount of component (a) used.
- any hydroxyl-containing ester of acrylic acid or methacrylic acid or a mixture of such monomers can be used as component (a).
- examples include: hydroxyalkyl esters of acrylic acid, e.g. Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, especially 4-hydroxybutyl acrylate; Hydroxyalkyl esters of methacrylic acid, e.g. Hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, in particular 4-hydroxybutyl methacrylate; Reaction products from cyclic esters, e.g. Epsilon-caprolactone and hydroxyalkyl esters of acrylic acid or methacrylic acid.
- hydroxyalkyl esters of acrylic acid e.g. Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, especially 4-hydroxybutyl methacrylate
- composition of component (a) is preferably selected so that when component (a) is polymerized alone, a polyacrylate resin having a glass transition temperature of -50 to +70, preferably -30 to + 50 ° C. is obtained.
- the glass transition temperature can be determined by the person skilled in the art with the aid of the formula
- W n weight fraction of the nth monomer
- TQ n glass transition temperature of the homopolymer from the nth monomer
- any aliphatic or cycloaliphatic esters of acrylic acid or methacrylic acid having at least 4 carbon atoms in the alcohol radical or a mixture of such monomers can be used as component (b).
- examples include: aliphatic esters of acrylic and methacrylic acid with 4 to 20 C atoms in the alcohol residue, such as e.g. n-butyl, iso-butyl, tert-butyl, 2-ethylhexyl, stearyl and lauryl acrylate and methacrylate as well as cycloaliphatic esters of acrylic and methacrylic acid such as.
- B. cyclohexyl acrylate and cyclohexyl methacrylate is preferably selected so that when component (b) is polymerized alone, a polyacrylate resin having a glass transition temperature of 10 to 100, preferably 20 to 60 ° C. is obtained.
- any ethylenically unsaturated carboxylic acid or a mixture of ethylenically unsaturated carboxylic acids can be used as component (c).
- Acrylic acid and / or methacrylic acid are preferably used as component (c).
- any ethylenically unsaturated monomer different from (a), (b) and (c) or a mixture of such monomers can be used as component (d).
- monomers which can be used as component (d) are: vinylaromatic hydrocarbons, such as styrene, alpha-alkylstyrene and ninyltoluene, amides of acrylic acid and methacrylic acid, such as, for example, methacrylamide and acrylamide, nitriles of methacrylic acid and acrylic acid; Vinyl ethers and vinyl esters or polysiloxane macromonomers as described in the patents DE-A-38 07 571, DE-A 3706095, EP-B-0 358 153, US-A 4,754,014, DE-A 44 21 823 or WO 92/22615 can be described.
- component (d) Vinylaromatic hydrocarbons, in particular styrene, are preferably used as component (d).
- the composition of component (d) is preferably selected so that when component (d) is polymerized alone, a resin having a glass transition temperature of 70 to 120, preferably 80 to 100 ° C. is obtained.
- the binders are contained in the coating material in an amount of 10 to 90% by weight, particularly preferably 15 to 80% by weight and in particular 20 to 70% by weight, in each case based on the total solids content of the coating material.
- suitable (co) polymers are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (meth) acrylate copolymers.
- suitable polyaddition resins and / or polycondensation resins are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, in particular polyesters polyurethanes.
- the (meth) acrylate (co) polymers have particular advantages and are therefore used with particular preference.
- the self-crosslinking binders contain reactive functional groups which can undergo crosslinking reactions with groups of their type or with complementary reactive functional groups.
- the externally crosslinking binders contain reactive functional groups which are complementary with reactive functional groups which are used in crosslinking agents. there are crosslinking reactions. Examples of suitable complementary reactive functional groups to be used according to the invention are summarized in the following overview.
- the variable R stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R and R stand for the same or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.
- the selection of the respective complementary groups depends on the one hand on the fact that they do not cause any undesired reactions during production, storage or application, in particular no premature crosslinking. tion, shrinkage and / or may not interfere with or inhibit curing with actinic radiation, and on the other hand in which temperature range the crosslinking should take place.
- thio, hydroxyl, N-methylolamino, N, alkoxymethylamino, imino, carbamate, allophanate and / or carboxyl groups preferably hydroxyl or carboxyl groups, on the one hand, and preferably crosslinking agents with anhydride, carboxyl , Epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, carbonate, amino, hydroxy and / or beta-hydroxyalkylamide groups, preferably epoxy, beta-hydroxyalkylamide, blocked isocyanate, Urethane or alkoxymethylamino groups, on the other hand applied.
- Self-crosslinking binders contain, in particular, methylol, methylol ether and / or N-alkoxymethylamino groups.
- the functionality of the binders with respect to the reactive functional groups described above can vary very widely and depends in particular on the crosslinking density that is to be achieved and / or on the functionality of the crosslinking agent used in each case.
- the OH number can also be 15 to 300, preferably 30 to 250, particularly preferably 50 to 200, very particularly preferably 70 to 180 and in particular 80 to 170 mg of KOH / g lie.
- the above-described complementary functional groups can be incorporated into the binders by the customary and known methods in polymer chemistry. This can be done, for example, by incorporating monomers which carry the corresponding reactive functional groups and / or using polymer-analogous reactions.
- Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid which are derived from an alkylene glycol which is esterified with the acid, or which can be obtained by reacting the alpha-beta-olefinically unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide are, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3 -Hydroxybutyl-, 4-hydroxybutyl acrylate, - methacrylate, -ethacrylate, -crotonate, -maleinate, -fumarate or - itaconate; or hydroxycyclo
- olefinically unsaturated alcohols such as allyl alcohol
- Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;
- (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl-, N-methylol-, NN-dimethylol-, N-methoxymethyl-, N, N- Di (methoxymethyl) -, N-ethoxymethyl- and / or N, N-di (ethoxyethyl) - (meth) acrylic acid amide;
- Acrylic acid methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;
- Vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or vinylbenzenesulfonic acid (all isomers).
- Monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid or allyl glycidyl ether. They are preferably used to prepare the (meth) acrylate copolymers preferred according to the invention, in particular those containing hydroxyl groups and / or carbamate groups.
- suitable monomer units for introducing reactive functional groups into polyester or polyester-polyurethanes are 2,2-dimethylolethyl- or propylamine, which are blocked with a ketone, the resulting ketoxime group being hydrolyzed again after installation; or compounds which contain two hydroxyl groups or two primary and / or secondary amino groups and at least one acid group, in particular at least one carboxyl group and / or at least one sulfonic acid group, such as dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxybenzoic acid, 2,2-dimethylolacetic acid, 2.2 - dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-
- the binders of the dual-cure mixtures according to the invention furthermore contain on average at least one, preferably at least two, group (s) with at least one bond (s) which can be activated with actinic radiation per molecule.
- a bond which can be activated with actinic radiation is understood to mean a bond which becomes reactive when irradiated with actinic radiation and which undergoes polymerisation reactions and / or crosslinking reactions with other activated bonds of its kind which take place according to radical and / or ionic mechanisms.
- suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds.
- the carbon-carbon double bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention. For the sake of brevity, they are referred to below as "double bonds".
- the group preferred according to the invention contains one double bond or two, three or four double bonds. If more than one double bond is used, the double bonds can be conjugated. According to the invention, however, it is advantageous if the double bonds are isolated, in particular each individually individually in the one in question here Group. According to the invention, it is particularly advantageous to use two, in particular one, double bond.
- the dual-cure binder contains at least one of the groups described above which can be activated with actinic radiation.
- the functionality of the binder in this regard is an integer, i.e. for example two, three, four, five or more, or non-integer, i.e. for example 2.1 to 10.5 or more. Which functionality you choose depends on the requirements placed on the respective coating agent.
- the groups are structurally different from one another or of the same structure.
- Suitable groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, but especially acrylate groups.
- the groups are preferably via urethane, urea, allophanate, ester, ether and / or amide groups, but especially via ester groups. pen, bound to the respective basic structures of the binders. This is usually done by customary and known polymer-analogous reactions, such as the reaction of pendant glycidyl groups with the above-described olefinically unsaturated monomers which contain an acid group, of pendant hydroxyl groups with the halides of these monomers, of isocyanates containing hydroxyl groups with double bonds, such as vinyl isocyanate, methacryloyl isocyanate and / or 1 - (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI® from CYTEC) or of isocanate groups with the monomers described above containing hydroxyl groups.
- Suitable binders which are curable purely with actinic radiation come from the oligomer and / or polymer classes of the (meth) acrylic-functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and phosphazene acrylates and the like corresponding methacrylates. It is preferred to use binders which are free from aromatic structural units.
- Urethane (meth) acrylates, phosphazene (meth) acrylates and / or polyester (meth) acrylates are therefore preferably used, particularly preferably urethane (meth) acrylates, in particular aliphatic urethane (meth) acrylates.
- the urethane (meth) acrylates are 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 subsequent reaction of the remaining free isocyanate groups with at least one hydroxyal kyl (meth) acrylate or hydroxyalkyl ester 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 OH groups of the hydroxyalkyl esters of the ethylenically unsaturated carboxylic acids are present in a stoichiometric amount in relation to the free isocyanate groups of the prepolymer from isocyanate and chain extender.
- the urethane (meth) acrylates by first reacting part 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 OH 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 then be reacted with a diamine.
- 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.
- urethane (meth) acrylates examples include the following commercially available polyfunctional aliphatic urethane acrylates:
- Suitable polyphosphazene (meth) acrylate is the phosphazene dimethacrylate from Idemitsu, Japan.
- Reactors for the copolymerization are the customary and known stirred tanks, stirred tank cascades, tubular reactors, loop reactors or Taylor reactors, as described, for example, in the patents and patent applications DE 1 071 241 B1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, volume 50, number 9, 1995, pages 1409 to 1416.
- polyesters and alkyd resins are, for example, still in the standard work Ullmanns Encyclopedia of Industrial Chemistry, 3rd edition, volume 14, Urban & Schwarzenberg, Kunststoff, Berlin, 1963, pages 80 to 89 and pages 99 to 105, as well as in the books : "Resines Alkyd-Polyester” by J. Bourry, Paris, Dunod Verlag, 1952, "Alkyd Resins” by CR Martens, Reinhold Publishing Corporation, New York, 1961, and "Alkyd Resin Technology” by TC Patton, Intersience Publishers, 1962.
- polyurethanes and / or acrylated polyurethanes are described, for example, in patent applications EP 0 708 788 A1, DE 44 01 544 A1 or DE 19534 361 A1.
- suitable crosslinking agents are
- Polyisocyanates with 2 to 5 isocyanate groups per molecule and with viscosities of 100 to 10,000, preferably 100 to 5000 and in particular 100 to 2000 mPas (at 23 ° C.) are preferably used. If necessary, small amounts of organic can still be added to the polyisocyanates
- Solvents preferably 1 to 25% by weight, based on pure polyisocyanate, are added in order to improve the incorporability of the isocyanate and, if necessary, to lower the viscosity of the polyisocyanate to a value within the range mentioned above
- Solvents suitable as additives are the polyisocyanates, for example ethoxyethyl propionate, amyl methyl ketone or butyl acetate.
- the polyisocyanates can be modified in a conventional and known manner to be hydrophilic or hydrophobic.
- isocyanate group-containing polyurethane prepolymers which can be prepared by reacting polyols with an excess of polyisocyanates and which are preferably low-viscosity.
- polyisocyanates are isocyanurate, biuret, allophanate, iminooxadiazindone, urethane, urea and / or uretdione groups containing polyisocyanates.
- Polyisocyanates containing urethane groups are, for example, by reacting some of the isocyanate groups with polyols, such as tri- methylolpropane and glycerin.
- Aliphatic or cycloaliphatic polyisocyanates in particular hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, dicyclohexylmethane-2,4'-diisocyanate or di-cyclohexylmethane-4,4'-diisocyanate, are preferably derived of dimer fatty acids, such as those sold by Henkel under the trade name DDI 1410, 1,8-diisocyanato-4-isocyanatomethyl-octane, 1,7-diisocyanato-4-isocyanatomethyl-heptane or 1-isocyanato-2- (3- isocyanatopropyl) cyclohexane or
- beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N'-tetrakis (2-hydroxypropyl) adipamide and / or
- Tris (alkoxycarbonylamino) triazines as are described in the patents US 4,939,213 A 1, US 5,084,541 A 1, US 5,288,865 A 1 or EP 0 604 922 A 1, or EP 0 624 577, or tris (alkoxycarbonylamino) triazines of the general formula
- the tris (methoxy, tris (butoxy and / or
- Tris (2-ethylhexoxycarbonylamino) triazines can be used.
- methyl-butyl mixed esters, the butyl-2-ethylhexyl mixed esters and the butyl esters are advantageous. Compared to the pure methyl ester, these have the advantage of better solubility in polymer melts and also have less tendency to crystallize out.
- beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N'-tetrakis (2-hydroxypropyl) adipamide,
- Siloxanes in particular siloxanes with at least one trialkoxy or dialkoxysilane group,
- suitable additives are in particular thermally curable reactive diluents such as positionally isomeric diethyl octanediols or hydroxyl group-containing hyperbranched compounds or dendrimers;
- alkylene glycol di (meth) acrylate examples include alkylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpro - pantri (meth) acrylate, trimethylolpropane di (meth) acrylate, styrene, vinyl toluene, divinylbenzene, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxyethoxyethylaethyl , N-vinylpyrrolidone, phenoxyeth
- the two acrylate groups can be separated by a polyoxibutylene structure.
- 1, 12-Dodecyl diacrylate and the reaction product of 2 moles can also be used
- Acrylic acid with one mole of a dimer fatty alcohol which generally has 36 carbon atoms.
- Mixtures of the monomers mentioned are also suitable;
- Crosslinking catalysts such as dibutyltin dilaurate, lithium decanoate or zinc octoate, organic sulfonic acids blocked with amines, quaternary ammonium compounds, amines, imidazole and imidazole derivatives such as 2-styrylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole and 2-butylolazole as described in Belgian Patent No.
- phosphonium catalysts such as ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphoniumthiocyanate, ethyltriphenylphosphonium acetate-acetic acid complex, tetrabutidylphosphonium tetrabutidylphosphonium tetrabutidylphosphonium
- Tetrabutylphosphonium acetate-acetic acid complex as described, for example, in US Pat. Nos. 3,477,990 A1 or 3,341,580 A1;
- thermolabile free radical initiators such as organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzopinole silyl ethers;
- Antioxidants such as hydrazines and phosphorus compounds
- UV absorbers such as triazines and benzotriphenol
- Light stabilizers such as HALS compounds, benzotriazoles or oxalanilides
- Radical scavengers and polymerization inhibitors such as organic phosphites or 2,6 di-tert-butylphenol derivatives
- wetting agents such as siloxanes, fluorine-containing compounds, carboxylic acid ester, phosphoric acid ester, polyacrylic acids and their copolymers or polyurethanes, as described, for example, in detail in the
- Patent application DE 198 35 296 A 1 are described, in particular in connection with the associative thickeners based on polyurethane;
- Adhesion promoters such as tricyclodecanedimethanol
- film-forming aids such as cellulose derivatives
- Deaerators such as diazadicycloundecane or benzoin;
- rheology-controlling additives such as those known from the patent specifications WO 94/22968, EP 0 276 501, EP 0 249 201 A1 or WO 97/12945; cross-linked polymeric microparticles, such as those for example, are disclosed in EP 0 008 127 A1; inorganic layered silicates such as aluminum-magnesium-silicates, sodium-magnesium and sodium-magnesium-fluorine-lithium layered silicates of the montmorillonite type; Silicas such as aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or poly- acrylates; or associative thickeners based on polyurethane, as described in Rö
- the constituents are preferably selected such that the cured mixtures according to the invention have a storage module E 'in the rubber-elastic range of at least 10 ⁇ .6 Pa and a loss factor tan ⁇ at 20 ° C of at most 0.10, the storage module E ' and the loss factor having dynamic mechanical thermal analysis on free films with a layer thickness of 40 + 10 ⁇ m.
- the coating materials, adhesives and sealants can by the in German patent application DE 199 24 171 A1, page 9, lines 33 to 54, or
- German patent application DE 199 20 799 A1 page 3, lines 41 to 58, and page 10, lines 38 to 65,
- thermal curing and curing with actinic radiation are, for example, from
- German patent application DE 198 18 713 A1 column 10, page 31, to column 11, line 33,
- the coating materials of the invention are used in particular as clear lacquers and / or as color and / or effect coating materials for the production of clear lacquers and single and multi-layer, color and / or effect, electrically conductive, magnetically shielding and / or fluorescent coatings become.
- the stability of the coating materials, adhesives and sealing compounds according to the invention under static and dynamic conditions, in particular the stability of the ring line, and the run-off behavior during application and curing are excellent.
- the coating materials, adhesives and sealants according to the invention are outstanding for the coating, bonding and sealing of motor vehicle bodies, parts of motor vehicle bodies, motor vehicles indoors and outdoors, structures indoors and outdoors, doors, windows and furniture, and for painting, Bonding and sealing in the context of industrial painting, for example of small parts such as nuts, screws, rims or hubcaps, of coils, containers, packaging, electrical engineering components such as motor windings or transformer windings, and of white goods such as household appliances, boilers and radiators, suitable.
- the coatings according to the invention produced from the coating materials according to the invention are hard, scratch-resistant, weather-resistant, chemical-stable and, above all, of an extraordinarily high brilliance.
- the adhesive layers produced from the adhesives according to the invention permanently bond a wide variety of substrates bonded to them. There is no loss of adhesive strength even under extreme climatic conditions and / or strongly fluctuating temperatures.
- the seals produced from the sealing compounds according to the invention permanently seal the substrates sealed with them, even in the presence of highly aggressive chemicals.
- the substrates coated with the coatings according to the invention, bonded with the adhesive layers according to the invention and / or sealed with the seals according to the invention have an extraordinarily long service life and a particularly high utility value, which makes them particularly economical to manufacture and use.
- the clearcoats 1 to 4 according to the invention and the clearcoat C1 not according to the invention were prepared by mixing the constituents listed in Table 1 and homogenizing the resulting mixtures.
- Table 1 The material composition of the clearcoats 1 to 4 according to the invention and the clearcoat C1 not according to the invention Part of examples: Comparison test:
- Crosslinking agent melamine resin, Luwipal® 018 (BASF AG),
- Catalyst Nacure® 2500 blocked sulfonic acid
- Tinuvin® 384-2 0.7 0.7 0.7 0.7 0.7 0.7 0.7
- Aromatic solvents (added, not introduced)
- the runner lengths for a layer thickness of 55 ⁇ m were included
- the clearcoats 1 to 4 according to the invention in particular as regards hardness, scratch resistance, chemical resistance, weathering stability and etch resistance, were on a par with the clearcoat V1 not according to the invention.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10130069 | 2001-06-21 | ||
DE10130069A DE10130069A1 (de) | 2001-06-21 | 2001-06-21 | Physikalisch oder thermisch und/oder mit aktinischer Strahlung härtbare, lösemittelhaltige Gemische, Verfahren zu ihrer Herstellung und ihre Verwendung |
PCT/EP2002/006875 WO2003000809A1 (de) | 2001-06-21 | 2002-06-21 | Physikalisch oder thermisch und/oder mit aktinischer strahlung härtbare, lösemittelhaltige gemische, verfahren zu ihrer herstellung und ihre verwendung |
Publications (1)
Publication Number | Publication Date |
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EP1404767A1 true EP1404767A1 (de) | 2004-04-07 |
Family
ID=7689036
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP02743235A Withdrawn EP1404767A1 (de) | 2001-06-21 | 2002-06-21 | Physikalisch oder thermisch und/oder mit aktinischer strahlung härtbare, lösemittelhaltige gemische, verfahren zu ihrer herstellung und ihrer verwendung |
Country Status (6)
Country | Link |
---|---|
US (1) | US20040204524A1 (de) |
EP (1) | EP1404767A1 (de) |
CA (1) | CA2445732A1 (de) |
DE (1) | DE10130069A1 (de) |
MX (1) | MXPA03009402A (de) |
WO (1) | WO2003000809A1 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8568888B2 (en) | 2007-03-15 | 2013-10-29 | Nanovere Technologies, Inc. | Dendritic polyurethane coating |
US8206827B2 (en) | 2007-03-15 | 2012-06-26 | Nanovere Technologies, Llc | Dendritic polyurethane coating |
SG196808A1 (en) * | 2009-01-13 | 2014-02-13 | Tokuyama Corp | Coating composition, process for producing the composition, and laminate having a hard coat layer |
NL2006158C2 (nl) * | 2011-02-08 | 2012-08-09 | Fiets O Fit B V | Samenstelling van een acryllak, en een spuitbus gevuld met een dergelijke samenstelling. |
FR3063080B1 (fr) | 2017-02-23 | 2021-04-30 | Bostik Sa | Composition comprenant un polyester et film adhesif activable a basse temperature |
US10899920B2 (en) | 2018-09-14 | 2021-01-26 | Polysack Flexible Packaging Ltd. | Methods for forming high shrink wrap label sleeves |
US10858545B2 (en) | 2018-09-14 | 2020-12-08 | Polysack Flexible Packaging Ltd. | Shrink wrap labels for shaped articles |
CN114381180B (zh) * | 2020-10-20 | 2023-12-12 | 廊坊立邦涂料有限公司 | 一种单组分修补色漆及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4387194A (en) * | 1982-07-22 | 1983-06-07 | General Motors Corporation | High solids internally U.V. stabilized melamine cured urethane paint |
FR2664161A1 (fr) * | 1990-07-05 | 1992-01-10 | Poudres & Explosifs Ste Nale | Vernis a ongles nitrocellulosique sans toluene et procede de preparation. gel nitrocellulosique sans toluene. |
WO2000050523A1 (de) * | 1999-02-25 | 2000-08-31 | Basf Coatings Ag | Die verwendung von tricyclodecandimethanol zur herstellung von mehrschichtlackierungen |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH531989A (de) * | 1967-10-12 | 1972-12-31 | Degussa | Verfahren zur Herstellung von organisch modifizierten Kieselsäuren und Silikaten |
US3711344A (en) * | 1970-09-23 | 1973-01-16 | Us Army | Processing of crosslinked nitrocellulose propellants |
FR2511019B1 (fr) * | 1981-08-07 | 1986-02-28 | Norbert Segard | Perfectionnements apportes aux laques et peintures a sechage rapide |
DE3207936A1 (de) * | 1982-03-05 | 1983-09-15 | Herberts Gmbh, 5600 Wuppertal | Lackierungsverfahren unter verwendung von perlglanzpigmenten |
US5512273A (en) * | 1994-10-31 | 1996-04-30 | Almell, Ltd. | Top nail coat composition |
DE19908001A1 (de) * | 1999-02-25 | 2000-08-31 | Basf Coatings Ag | Hochkratzfeste Mehrschichtlackierung, Verfahren zu ihrer Herstellung und ihre Verwendung |
EP1050562A1 (de) * | 1999-05-04 | 2000-11-08 | Fina Research S.A. | Zusammensetzung mit niedrigem Aromatengehalt |
DE19924171A1 (de) * | 1999-05-25 | 2000-11-30 | Basf Coatings Ag | Beschichtungsstoff mit einer Mischung aus mindestens einem Netzmittel und Harnstoffen und/oder Harnstoffderivaten als Thixotropiermittel |
DE19924172A1 (de) * | 1999-05-25 | 2000-11-30 | Basf Coatings Ag | Beschichtungsstoff mit einer Mischung aus Kieselsäuren und Harnstoff und/oder Harnstoffderivaten |
DE19924674C2 (de) * | 1999-05-29 | 2001-06-28 | Basf Coatings Ag | Thermisch und mit aktinischer Strahlung härtbarer Beschichtungsstoff und seine Verwendung |
DE19938759A1 (de) * | 1999-08-16 | 2001-02-22 | Basf Coatings Ag | Beschichtungsstoff und seine Verwendung zur Herstellung hochkratzfester mehrschichtiger Klarlackierungen |
-
2001
- 2001-06-21 DE DE10130069A patent/DE10130069A1/de not_active Withdrawn
-
2002
- 2002-06-21 CA CA002445732A patent/CA2445732A1/en not_active Abandoned
- 2002-06-21 EP EP02743235A patent/EP1404767A1/de not_active Withdrawn
- 2002-06-21 MX MXPA03009402A patent/MXPA03009402A/es not_active Application Discontinuation
- 2002-06-21 WO PCT/EP2002/006875 patent/WO2003000809A1/de not_active Application Discontinuation
- 2002-06-21 US US10/478,925 patent/US20040204524A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4387194A (en) * | 1982-07-22 | 1983-06-07 | General Motors Corporation | High solids internally U.V. stabilized melamine cured urethane paint |
FR2664161A1 (fr) * | 1990-07-05 | 1992-01-10 | Poudres & Explosifs Ste Nale | Vernis a ongles nitrocellulosique sans toluene et procede de preparation. gel nitrocellulosique sans toluene. |
WO2000050523A1 (de) * | 1999-02-25 | 2000-08-31 | Basf Coatings Ag | Die verwendung von tricyclodecandimethanol zur herstellung von mehrschichtlackierungen |
Also Published As
Publication number | Publication date |
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CA2445732A1 (en) | 2003-01-03 |
US20040204524A1 (en) | 2004-10-14 |
MXPA03009402A (es) | 2005-08-16 |
DE10130069A1 (de) | 2003-01-16 |
WO2003000809A1 (de) | 2003-01-03 |
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