EP1218459A1 - Mit aktinischer strahlung aktivierbare bindungen enthaltendes festes stoffgemisch und seine verwendung - Google Patents
Mit aktinischer strahlung aktivierbare bindungen enthaltendes festes stoffgemisch und seine verwendungInfo
- Publication number
- EP1218459A1 EP1218459A1 EP00971308A EP00971308A EP1218459A1 EP 1218459 A1 EP1218459 A1 EP 1218459A1 EP 00971308 A EP00971308 A EP 00971308A EP 00971308 A EP00971308 A EP 00971308A EP 1218459 A1 EP1218459 A1 EP 1218459A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- groups
- solid
- compound
- solid mixture
- meth
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0209—Multistage baking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3253—Polyamines being in latent form
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/0263—After-treatment with IR heaters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- Solid substance mixture containing bonds which can be activated with actinic radiation and its use
- the present invention relates to new solid substance mixtures, the bonds which can be activated with actinic radiation and at least two different substances
- the present invention also relates to a new one
- the present invention relates to new coating materials, adhesives or
- the present invention relates to a new method for
- Coating materials, adhesives or sealants are used.
- the present invention relates to new primed or unprimed substrates which contain new coatings, adhesives and / or seals.
- actinic radiation means electromagnetic radiation such as X-rays, UV radiation, visible light or near IR light (NIR) or nuclear radiation such as electron beams.
- electromagnetic radiation such as X-rays, UV radiation, visible light or near IR light (NIR) or nuclear radiation such as electron beams.
- NIR near IR light
- nuclear radiation such as electron beams.
- This thermal polymerization leads to problems when working up the solids into powder coatings, for which multiple melting processes are usually necessary.
- the premature thermal polymerization is even more unpleasant when the powder coatings are melted onto the substrates before being irradiated with actinic radiation.
- polymerization inhibitors such as phenothiazine or hydroquinone can prevent the undesired premature thermal polymerization, but at the same time the reactivity when exposed to actinic radiation is reduced to such an extent that technically uninteresting long exposure times resulted.
- German patent application DE-A-24 36 186 or US Pat. No. 3,974,303 describe powdery and thermoplastic polymers which have 0.5 to 3.5 polymerizable unsaturated double bonds per 1000 molecular weight and their use as radiation-curable binders.
- a (mem) acrylate-functionalized polyurethane is described which is produced from tolylene diisocyanate, 2-hydroxyethyl methacrylate and trimethylolpropane in a molar ratio of 3: 3: 1 in the melt.
- the (mem) acrylate-functionalized polyurethane has a melting point of about 65 ° C. and a polymerizable double bond content of 2.9 double bonds per 1,000 molecular weight.
- European patent application EP-A-0 636 669 describes mixtures of unsaturated polyesters or (me ⁇ ) acrylate-functionalized polyacrylates, the polyacrylates being obtained in a conventional polymerization, and polyurethanes functionalized with vinyl ethers or (meth) acrylic esters as crosslinking agents.
- the examples show only mixtures of polyesters and vinyl ether urethanes.
- the vinyl ether urethanes are produced in chloroform as a solvent.
- the polyurethanes are produced in ethyl acetate as a solvent, after which the solvent must be evaporated in vacuo at low temperatures. No information is given on stabilization against premature thermal crosslinking of the melts without negatively influencing the reactivity during radiation curing. No teaching is given to solve the further complex problems described above in the development of technically usable radiation-curable powder coatings.
- European patent EP-A-0 783 534 discloses (meth) acrylate-functionalized polyurethanes which are obtained with the use of monofunctional hydroxy compounds without unsaturated groups. Although this lowers the viscosity, these non-reactive terminal groups reduce the reactivity when curing with actinic radiation. Coatings thermally crosslinked with peroxides are desired. No information is given on stabilization against premature thermal crosslinking without negatively influencing the reactivity during radiation curing. No teaching is given to solve the further complex problems described above in the development of technically usable UV powder coating systems.
- the object of the present invention is to provide new solid substance mixtures which contain bonds which can be activated with actinic radiation and at least two compounds which are different from one another and which no longer have the disadvantages of the prior art, but which can be prepared in a simple manner, by comparison melt at low temperatures, are stable in the melt and have a low melt viscosity, do not tend to premature thermal crosslinking, show high reactivity during curing with actinic radiation, do not block in powder form, but flow freely, and for the production of new, in particular powdery coating materials, adhesives and sealants are very suitable, the new coating materials, adhesives and sealants being used to provide coatings, adhesives and seals which are highly hard, elastic, scratch-resistant and chemical-resistant speed, weather stability and especially the coatings, especially the paintwork, should have a very smooth surface and a very good overall visual impression. Accordingly, the new solid mixture containing
- Group (a) with at least one bond which can be activated by actinic radiation and
- coating materials which are produced with the aid of the substance mixtures according to the invention and are referred to below as "coating materials, adhesives and sealants according to the invention".
- Adhesive and / or at least one sealant according to the invention in the mold Adhesive and / or at least one sealant according to the invention in the mold
- the new process for the production of coatings, adhesive layers and seals for primed or unprimed substrates from the coating materials, adhesives and sealants according to the invention is referred to as the “process according to the invention”.
- Coatings, adhesive layers and sealants according to the invention are referred to.
- the new primed or unprimed substrates were found which have at least one coating, adhesive layer and / or seal according to the invention and are collectively referred to below as "substrates according to the invention".
- 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 polymerization reactions and / or crosslinking reactions with other activated bonds of its type 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 first essential component of the mixture of substances according to the invention is at least one solid (meth) acrylate copolymer (A), in particular a methacrylate copolymer (A).
- Mn has a number average molecular weight Mn of 850 to 10,000, preferably 900 to 9,500, preferably 950 to 9,000, particularly preferably 950 to 8,500, very particularly preferably 1,000 to 8,000 and in particular 1,000 to 7,500. Its non-uniformity in the molecular weight Mw / Mn is 1.0 to 5.0, preferably 1.0 to 4.5, in particular 1.0 to 4.0.
- the (meth) acrylate copolymer (A) to be used according to the invention contains at least one group (a) with at least one double bond.
- group (a) 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 in group (a). According to the invention, it is particularly advantageous to use two, in particular one, double bond.
- the (meth) acrylate copolymer (A) contains at least one group (a) on average.
- the functionality of the (meth) acrylate copolymer (A) is an integer, that is, for example, one, two, three, four, five or more, or not an integer, that is, for example, 1.1 to 10.5 or more is. Which functionality one chooses depends on the one hand on the stoichiometric ratios of the starting products of the (meth) acrylate copolymer (A), which on the other hand depends on its application purposes.
- the at least two groups (a) are structurally different from one another or of the same structure.
- groups (a) are used which differ from two, three, four or more, but in particular two, monomer classes derived.
- suitable groups (a) are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups.
- the solid according to the invention can be a combination of two, three, four or more, but in particular two, of the above-mentioned groups (a), for example
- the combinations of the (meth) acrylate group, in particular the acrylate group, with at least one, in particular one, further type of groups (a) are advantageous and are therefore used with preference.
- (meth) acrylate groups in particular acrylate groups, are preferably used.
- the (meth) acrylate copolymers (A) can be prepared by any copolymerization method. According to the invention, it is advantageous to use them
- the radical high-temperature polymerization is preferably carried out at temperatures of 140 to 220, preferably 145 to 210 and in particular 150 to 200 ° C. in concentrated solution or in bulk in the melt.
- 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 benzopinacol silyl ethers are preferably used, which provide radicals at temperatures of 140 to 200 ° C.
- Suitable methacrylates (ml) which do not carry reactive functional groups (b) are alkyl or cycloalkyl methacrylic acid with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl -, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or - methacrylate; cycloaliphatic methacrylic acid esters, especially cyclohexyl, isobomyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene methanol or tert-butylcyclohexyl methacrylate; Oxaalkyl methacrylate or - oxacycloalkyl esters such as ethyl triglycol methacrylate and
- These can be used in minor amounts of higher-functionality alkyl or cycloalkyl methacrylic acid, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane 1, 5-diol, hexane 1, 6-diol, octahydro-4,7 -methano-1 H-indene-dimethanol- or cyclohexane-1,2-, -1,3- or -1,4-diol-dimethacrylate; trimethacrylate; or pentaerythritol tetramethacrylate; contain.
- minor amounts of higher-functional monomers (ml) are to be understood as amounts which do not lead
- Suitable monomers (m2) which do not carry any reactive functional groups (b) are alkyl or cycloalkyl esters of acrylic acid with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl -, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or acrylate; cycloaliphatic acrylic acid esters, especially cyclohexyl, isobomyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene-methanol or tert-butylcyclohexyl acrylate; Oxaalkyl methacrylate or oxacycloalkyl ester such as ethyl triglycol acrylate and methoxy oligoglycol acrylate with a molecular weight M
- higher-functional alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1,5-diol, hexane-1,6-diol, octahydro-4,7- methano-1H-indene-dimethanol or cyclohexane-1,2-, 1,3- or 1,4-diol dicrylate; trimethylolpropane triacrylate; or pentaerythritol tetraacrylate; contain.
- higher-functional monomers (m2) are subordinate amounts of higher-functional monomers (m2) to understand which do not lead to crosslinking or gelling of the polyacrylate resins.
- the branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be crack products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and or cycloaliphatic olefins. When such olefins are reacted with formic acid or with carbon monoxide and water, a
- carboxylic acids in which the carboxyl groups are predominantly located on a quaternary carbon atom.
- Other olefinic starting materials are e.g. Propylene trimer, propylene tetramer and diisobutylene.
- the vinyl esters can also be prepared from the acids in a manner known per se, e.g. by allowing the acid to react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used.
- Olefins such as ethylene, propylene, but-l-ene, pent-1-ene, hex-l-ene,
- vinyl aromatic hydrocarbons such as styrene, alpha-alkylstyrenes, especially alpha-methylstyrene, arylstyrenes, in particular
- Vinyl compounds such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,
- Mn from 1,000 to 40,000, preferably from 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, such as they in DE-A-38 07 571 on pages 5 to 7, DE-A 37 06 095 in columns 3 to 7, the
- High-temperature polymerization formed (meth) acrylate copolymer is reacted in a polymer-analogous reaction to the (meth) acrylate copolymer (A) to be used according to the invention.
- the polymer-analogous reaction is preferably carried out in a reaction extruder at temperatures from 90 to 140 ° C., residence times from 3 to 20 minutes and conversions from 50 to 100%.
- variable R stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic
- olefinically unsaturated acids such as acrylic acid, methacrylic acid, ethacrylic acid or crotonic acid, maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono (meth) acryloyloxyethyl ester;
- (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl -, N, N-
- N-ethyl N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl, N, N-dibutyl, N-cyclohexyl, N, N-cyclohexyl-methyl -, N-hydroxymethyl, N-butoxymethyl and / or N-
- Monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid or crotonic acid;
- Carbamoyloxyethyl (meth) acrylate and or
- the (meth) acrylate copolymers (A) in the mixtures according to the invention are preferably present in an amount of 5.0 to 95, preferably 10 to 90, particularly preferably 15 to 85, very particularly preferably 20 to 80 and, based on the mixture according to the invention contain in particular 25 to 75 wt .-%.
- the further essential component of the mixture of substances according to the invention is at least one solid compound (B). It contains a basic structure and, bound to it, a statistical average of more than one, preferably more than 1.3, preferably more than 1.5, particularly preferably more than 1.6, very particularly preferably more than 1.8 and in particular more than 2 grappa (s) (a) with at least one bond which can be activated with actinic radiation, in particular a double bond, per molecule.
- the groups (a) of the solid compounds (B) are via urethane, ester, ether and / or amide groups, but in particular via urethane groups. bound to the basic structure of the solid according to the invention.
- the following two linking structures I and II can be considered:
- Both linking structures I and II or only one of them can be present in the solid compound (B).
- structure I is advantageous because of the larger number of starting products available and their comparatively simpler manufacture, and is therefore preferably used according to the invention.
- the groups (a) are bound to the basic structure at the end and / or laterally. Which type of connection is chosen depends in particular on whether the functional groups in the grand structure with which the starting products of groups (a) are able to react are terminal or lateral. Terminal groups (a) often have a higher reactivity than lateral groups (a) due to the lack of steric shielding and are therefore used with preference.
- the reactivity of the solid according to the invention can be specifically controlled via the ratio of terminal and lateral groups (a), which is a further particular advantage of the solid according to the invention.
- the basic structure of the solid compound (B) is low molecular weight, oligomeric and / or polymeric. That is, the solid compound (B) is a low molecular compound, an oligomer or a polymer. Or else the solid compound (B) has low molecular weight and oligomeric, low molecular weight and polymeric, oligomeric and polymeric or low molecular weight, oligomeric and polymeric basic structures, ie it is a mixture of low molecular weight compounds and oligomers, low molecular weight compounds and polymers, oligomers and polymers or low molecular weight compounds, oligomers and polymers.
- oligomers are understood to mean resins which contain at least 2 to 15 recurring monomer units in their molecule.
- polymers are understood to be resins which contain at least 10 recurring monomer units in their molecule.
- the low molecular weight, oligomeric or polymeric basic structure contains or consists of aromatic, cycloaliphatic and or aliphatic structures or building blocks. It preferably contains or consists of cycloaliphatic and / or aliphatic structures, in particular cycloaliphatic and aliphatic structures.
- aromatic structures are aromatic and heteroaromatic rings, especially benzene rings.
- cycloaliphatic structures are cyclobutane, cyclopentane, cyclohexane, cycloheptane, norbonane, camphane, cyclooctane or tricyclodecane rings, in particular cyclohexane rings.
- Examples of aliphatic structures are linear or branched alkyl chains with 2 to 20 carbon atoms or chains, such as those resulting from the (co) polymerization of olefinically unsaturated monomers.
- the basic structure in particular the oligomeric and / or polymeric basic structure, can also contain olefinically unsaturated double bonds.
- the basic structure in particular the oligomeric and or polymeric basic structure, has a linear, branched, hyperbranched or dendrimeric structure.
- It can contain multi-bonded, in particular double-bonded, functional groups (d), by means of which the structures or building blocks described above are linked together to form the basic structure. These are generally selected so that they do not interfere with, or even completely prevent, polymerization and / or crosslinking initiated by actinic radiation and or thermally.
- Suitable functional groups are ether, thioether, carboxylic acid ester, thiocarboxylic acid ester, carbonate, thiocarbonate, phosphoric acid ester, thiophosphoric acid ester, phosphonic acid ester, Thiophosphonic acid ester, phosphite, thiophosphite, sulfonic acid ester, amide, amine, thioamide, phosphoric acid amide, thiophosphoric acid amide, phosphonic acid amide, thiophosphonic acid amide, sulfonic acid amide, imide, urethane, hydrazide, urea, thi , Carbonyl, thiocarbonyl, sulfone, sulfoxide or siloxane groups.
- the ether, carboxylic acid ester, carbonate, carboxylic acid amide, urea, urethane, imide and carbonate groups are advantageous and are therefore used with preference.
- Advantageous oligomeric and polymeric basic fractures are thus derived from random, alternating and / or block-like linear, branched, hyperbranched, dendrimeric and / or comb-like (co) polymers of ethylenically unsaturated monomers, 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 “Polyadditionharze (polyadducts)", as well as pages 463 and 464, "Polycondensates”, “Polycondensation” and “Polycondensation Resins”.
- Examples of highly suitable (co) polymers are poly (meth) acrylates and partially saponified polyvinyl esters.
- polyesters examples include polyesters, alkyds, polyurethanes, polyester-polyurethanes, polylactones, polycarbonates, polyethers, polyester-polyethers, epoxy resin-amine adducts, polyureas, polyamides or polyimides.
- polyesters, polyester-polyethers, polyurethanes and polyester-polyurethanes are particularly advantageous and are therefore used with very particular preference in accordance with the invention.
- the basic structure can also carry the reactive functional groups (b) described above, which can undergo radical, ionic and / or thermally initiated crosslinking reactions with reactive functional groups (b) of their own type or with other, complementary, functional groups (c).
- the complementary functional groups (b) and (c) can be present in one and the same basic structure, which is the case with so-called self-crosslinking systems.
- the functional grapples (c) can, however, also be present in a further constituent, for example a crosslinking agent, which differs materially from the solid according to the invention, which is the case with so-called externally crosslinking systems.
- Reactive functional groups (b) and (c) are used in particular when the solid according to the invention is intended to be curable with actinic radiation and thermally (dual cure). They are selected so that they do not interfere with, or even completely prevent, the polymerization of the olefinic double bonds of groups (a) initiated with actinic radiation.
- reactive functional groups (b) and (c) which add to olefinically unsaturated double bonds can be used in minor, ie in non-interfering, amounts.
- reactive complementary groups (b) and / or (c) are also used, they are preferably present in the solid according to the invention in an amount corresponding to an average of 0.1 to 4 groups per molecule.
- a particularly advantageous solid compound (B) contains, in addition to the grapples (a) described above and optionally (b), (c), (d), and / or (f), at least one chemically bound stabilizer (e).
- the particularly advantageous solid compound (B) 0.01 to 1.0 mol%, preferably 0.02 to 0.9 mol%, particularly preferably 0.03 to 0.85 mol%, very particularly preferably 0.04 to 0.8 mol%, and in particular 0.05 to 0.75 mol%, especially 0.06 to 0.7 mol%, in each case based on the bonds present in the solid compound (B) which can be activated with active radiation, especially double bonds, of the chemically bound stabilizer (s).
- the chemically bound stabilizer (e) is a compound that is or provides steric hindered nitroxyl radicals (> NO * ) that scavenge free radicals in the modified Denisov cycle.
- Suitable chemically bound stabilizers are HALS compounds, preferably 2,2,6,6-tetraalkylpiperidine derivatives, in particular 2,2,6,6-tetramethylpiperidine derivatives, the nitrogen atom of which is substituted by an oxygen atom, an alkyl group, alkylcarbonyl group or alkyl ether group.
- HALS compounds preferably 2,2,6,6-tetraalkylpiperidine derivatives, in particular 2,2,6,6-tetramethylpiperidine derivatives, the nitrogen atom of which is substituted by an oxygen atom, an alkyl group, alkylcarbonyl group or alkyl ether group.
- the chemically bound stabilizer (e) can also be contained in the solid (meth) acrylate copolymer (A). The above applies accordingly.
- the basic structure can also contain chemically bound photoinitiators and or photocoinitiators (f).
- suitable chemically bound photoinitiators are those of the Norrish II type, the mechanism of which is based on an intramolecular variant of the hydrogen abstraction reactions, as occurs in a variety of ways in photochemical reactions (examples here are from Römpp Chemie Lexikon, 9th extended and revised edition, Georg Thieme Verlag Stuttgart, Volume 4, 1991, referenced) or cationic photoinitiators (for example, see here Römpp Lexikon Lacke und Druckmaschinetician, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446, referenced), in particular benzophenones, benzoins or benzoin ethers or phosphine oxides.
- photocoinitiator is anthracene. If the chemically bound photoinitiators and / or photocoinitiators (f) are also used, they are present in the solid compound (B) in an amount corresponding to a statistical average of 0.01 to 2.0 groups (f) per molecule.
- the chemically bound photoinitiators and / or photocoinitiators (f) can also be contained in the solid (meth) acrylate copolymer (A). The above applies accordingly.
- the production of the basic structures has no special features in terms of method, but takes place with the aid of the customary and known synthesis methods of low molecular weight organic chemistry and / or polymer chemistry.
- the oligomeric and or polymeric basic structures which are very particularly preferred according to the invention and which are derived from polyesters, polyester-polyethers, polyurethanes and polyester-polyurethanes, but in particular from polyurethanes and polyester-polyurethanes, the usual and known methods of polyaddition and / or Polycondensation applied.
- the very particularly preferred polyurethanes and polyester polyurethanes are made from polyols and diisocyanates and, if appropriate, polyamines and amino alcohols.
- the polyols and diisocyanates and, if appropriate, the polyamines and amino alcohols are used in molar ratios to give hydroxyl-entrained or isocyanate-entrained polyurethanes or polyester-polyurethanes.
- Diisocyanates and optionally in minor amounts are preferred for the production of the polyurethanes and polyester polyurethanes Polyisocyanates used to carry out branches.
- minor amounts are to be understood as amounts which do not cause the polyurethanes and polyester-polyurethanes to gel during their production. The latter can also be prevented by using small amounts of monoisocyanates.
- suitable polyisocyanates are the isocyanurates of the diisocyanates described above.
- suitable polyisocyanates are polyurethane prepolymers containing isocyanate groups, which can be prepared by reacting polyols with an excess of polyisocyanates and are preferably low-viscosity. It is also possible to use polyisocyanates containing biuret, allophanate, aminooxadiazinedione, urethane, urea carbodiimide and / or uretdione groups.
- Polyisocyanates containing urethane groups are obtained, for example, by reacting some of the isocyanate groups with polyols, such as, for example, trimethylolpropane and glycerol.
- Examples of highly suitable monoisocyanates are phenyl isocyanate, cyclohexyl isocyanate or stearyl isocyanate.
- suitable polyols are saturated and unsaturated high molecular weight and low molecular weight polyols, in particular diols and, in minor amounts, triols or higher functional polyols for introducing branches.
- Suitable polyols are saturated or olefinically unsaturated polyester polyols which are obtained by reacting
- suitable polycarboxylic acids are aromatic, aliphatic and cycloaliphatic polycarboxylic acids. Aromatic and or aliphatic polycarboxylic acids are preferably used.
- aromatic polycarboxylic acids examples include phthalic acid, isophthalic acid, terephthalic acid, phthalic acid, isophthalic acid or terephthalic acid monosulfonate, or halophthalic acids, such as tetrachloro- or tetrabromophthalic acid, of which isophthalic acid is advantageous and is therefore used with preference.
- Suitable acyclic aliphatic or unsaturated polycarboxylic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid or dodecanedicarboxylic acid or maleic acid, fumaric acid or itaconic acid, of which adipic acid and glasic acid, sebacic acid, sebacic acid, sebum acid, sebum acid, sebic acid, sebum acid, sebic acid, sebum acid, sebic acid, sebum acid, sebic acid, sebum acid, sebic acid, sebic acid, sebum acid, sebic acid, sebic acid, sebum acid, sebic acid, sebic acid, sebum acid, sebic acid, sebum acid, sebic acid, sebum acid, sebic acid, sebum acid, sebic acid, sebic acid, sebum acid, sebic acid, sebum
- Suitable cycloaliphatic and cyclic unsaturated polycarboxylic acids are 1,2-cyclobutanedicarboxylic acid, 1,3-
- Cyclopentanedicarboxylic acid hexahydrophthalic acid, 1, 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, tricyclodecanedicarboxylic acid, tetrahydrophthalic acid, endomethylene tetrahydrophthalic acid or 4-methyltetrahydrophthalic acid.
- dicarboxylic acids can be used both in their ice and in their trans form and as a mixture of both forms.
- suitable polycarboxylic acids are polymeric fatty acids, in particular those with a dimer content of more than 90% by weight, which are also referred to as dimer fatty acids.
- esterifiable derivatives of the abovementioned polycarboxylic acids such as, for example, their mono- or polyvalent esters with aliphatic alcohols or polyols with 1 to 4 carbon atoms.
- anhydrides of the above-mentioned polycarboxylic acids can also be used if they exist.
- monocarboxylic acids can also be used together with the polycarboxylic acids, such as, for example, benzoic acid, tert-butylbenzoic acid, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid or stearic acid, other fatty acids of naturally occurring oils, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid or the adduct of dicyclic acid dehydridide and dicyclic acid adidide and dicyclic acid adidide in a molar ratio of 1: 1.
- suitable polyols are diols, triols, tetrols and sugar alcohols, but especially diols.
- the higher-functional polyols are usually used in minor amounts in addition to the diols in order to introduce branches into the polyester polyols. In the context of the present invention, minor amounts are to be understood as amounts which do not cause the polyester polyols to gel during their production.
- Suitable diols are ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,2-, 1,3-, 1,4- or 1.5 -Pentanediol, 1,2-, 1,3-, 1,4-, 1,5- or 1,6-hexanediol, hydroxypivalic acid neopentyl ester, neopentyl glycol, diethylene glycol, 1,2-, 1,3- or 1,4-cyclohexanediol , 1,2-, 1,3- or 1,4-cyclohexanedimethanol, trimethylpentanediol, ethyl butyl propanediol, bisphenol A, hydrogenated bisphenol A or the positionally isomeric diethyloctanediols. These diols can also be used as such for the production of the polyurethanes (A) to be used according to the invention.
- diols of the formula III or IV are diols of the formula III or IV:
- R 2 and R 3 each represent the same or different radical and represent an alkyl radical having 1 to 18 carbon atoms, an aryl radical or a cycloaliphatic radical, with the proviso that R and / or R must not be methyl;
- R 4 , R 5 , R 7 and R 8 each represent the same or different radicals and represent an alkyl radical with 1 to 6 C atoms, a cycloalkyl radical or an aryl radical and R 6 is an alkanediyl radical with 1 to 6 C atoms, represents an arylene radical or an unsaturated alkenediyl radical having 1 to 6 C atoms, and n is either 0 or 1.
- Suitable diols III of the general formula III are all propanediols of the formula in which either R 2 or R 3 or R 2 and R 3 are not the same methyl, such as 2-butyl-2-ethylpropanediol-1, 3, 2-butyl -2-methylpropanediol-1,3,2-phenyl-2-methylpropane-diol-1,3,2-propyl-2-ethylpropanediol-1,3,2-di-tert-butylpropanediol-1,3,2- Butyl-2- ⁇ ro ⁇ yl ⁇ ro ⁇ andiol-1, 3, l-dihydroxymethyl-bicyclo [2.2.
- diols IV of the general formula IV for example 2,5-dimethyl-hexanediol-2,5, 2,5-diethylhexanediol-2,5, 2-ethyl-5-methylhexanediol-2,5, 2,4-dimethylpentanediol-2 , 4, 2,3-dimethylbutanediol-2,3,1,4- (2 * -hydroxypropyl) benzene and 1,3- (2'-hydroxypropyl) benzene can be used.
- the diols mentioned above can also be used as such for the production of the polyurethanes and polyester polyurethanes.
- triols examples include trimethylolethane, trimethylolpropane or glycerol, in particular trimethylolpropane.
- Suitable tetrols are pentaerythritol or homopentaerythritol.
- Suitable higher functional polyols are sugar alcohols such as threitol, erythritol, arabitol, adonitol, xylitol, sorbitol, mannitol or dulcitol.
- the above-mentioned higher-functional polyols can also be used as such for the production of the polyurethanes and polyester-polyurethanes (cf. patent specification EP-A-0 339 433).
- monools can also be used.
- suitable monools are alcohols or phenols such as ethanol, propanol, n-butanol, sec-butanol, tert-butanol, amyl alcohols, hexanols, fatty alcohols, allyl alcohol or phenol.
- the polyester polyols can be prepared in the presence of small amounts of a suitable solvent as an entrainer.
- a suitable solvent as an entrainer z.
- suitable polyols are polybutadienes containing hydroxyl groups or polyurethanes.
- polyester diols which are obtained by reacting a lactone with a diol. They are characterized by the
- CHR9 CO- (CHR9) m - CH2-O -) - from.
- No substituent contains more than 12 carbon atoms. The total number of carbon atoms in the substituent does not exceed 12 per lactone ring. Examples include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid and / or hydroxystearic acid.
- the unsubstituted ### - caprolactone in which m has the value 4 and all R ⁇ substituents are hydrogen, is preferred.
- the reaction with lactone is started by low molecular weight polyols such as ethylene glycol, 1,3-propanediol, 1, 4-butanediol or dimethylolcyclohexane.
- low molecular weight polyols such as ethylene glycol, 1,3-propanediol, 1, 4-butanediol or dimethylolcyclohexane.
- other reaction components such as ethylenediamine, alkyldialkanolamines or even urea, can also be reacted with caprolactone.
- polylactam diols which are prepared by reacting, for example, ### - caprolactam with low molecular weight diols.
- polyester diols examples include the polycaprolactone diols, which are sold under the CAPA® brand by Solvay Interox.
- suitable polyols are polyether polyols, in particular with a number average molecular weight from 400 to 5000, in particular from 400 to 3000.
- Linear or branched polyether diols such as poly (oxyethylene) glycols, poly (oxypropylene) glycols and
- polyols can also be used as such for the production of the polyurethanes or polyester-polyurethanes.
- Polyamines and amino alcohols can be used to produce the polyurethanes and polyester polyurethanes, which bring about an increase in the molecular weight of the basic structure. It is essential here that the polyamines and amino alcohols are used in an amount such that free isocyanate groups or hydroxyl groups remain in the molecule.
- polyamines have at least two primary and / or secondary amino groups.
- Polyamines are essentially alkylene polyamines having 1 to 40 carbon atoms, preferably about 2 to 15 carbon atoms. They can carry substituents that have no hydrogen atoms that are reactive with isocyanate grapples. Examples are polyamines with a linear or branched aliphatic, cycloaliphatic or aromatic structure and at least two primary amino groups.
- diamines are hydrazine, ethylenediamine, propylene cuamin, 1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethylamine, 1,6-hexamethylenediamine, trimethylhexamethylenediamine, methanediamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane and aniinoethylenohanolamine.
- Preferred diamines are hydrazine, alkyl- or cycloalkyldiarnines such as propylenediamine and 1-ammo-3-aminomethyl-3,5,5-trimethyl-cyclohexane.
- polyamines which contain more than two amino groups in the molecule. In these cases, however, care must be taken, for example by using monoamines, that no crosslinked polyurethane resins are obtained.
- useful polyamines are diethylene triarnine, triethylene tetramine, dipropylene diamine and dibutylene triamine.
- An example of a monoamine is ethylhexylamine (cf. patent EP-A-0 089 497).
- Suitable amino alcohols are ethanolamine, diethanolamine or triethanolamine.
- the groups (a) described above to be used according to the invention are introduced with the aid of suitable starting products (a) during the preparation of the basic structure or after the production of the basic structure by polymer-analogous reactions, resulting in the solid according to the invention.
- linking urethane groups I and / or II described above are formed in the reaction of the starting products (a).
- the starting products (a) contain a hydroxyl group which reacts with the free isocyanate groups of the structure and / or the isocyanate groups of the other starting products to form the linking urethane groups I.
- the starting products (a) contain an isocyanate group which reacts with the hydroxyl groups of the basic structure and / or the hydroxyl groups of the other starting products to form the linking urethane groups II.
- the starting products (a) already contain a pre-formed linking urethane group I or II.
- these starting products (a) contain at least two, in particular two, reactive functional groups, which, together with suitable reactive functional groups, form part of the other starting products divalent functional groups (c) react.
- highly suitable reactive functional groups are the complementary reactive functional groups (e) and (f) described above, of which the hydroxyl groups and isocyanate groups are particularly advantageous and are used with very particular preference according to the invention.
- suitable starting products (a) for variant (i) are therefore customary and known monomers which carry at least one hydroxyl group per molecule, such as the monomers (m3) described above.
- the acrylates in particular 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl and 4-hydroxybutyl acrylate, especially 2-hydroxyethyl acrylate, are of particular advantage and are therefore used with very particular preference in accordance with the invention.
- diisocyanates described below preferably the linear diisocyanates, with Compounds which contain an isocyanate-reactive group, preferably one of the functional groups (b) or (c) described above, in particular a hydroxyl group, and at least one of the groups (a) described above, in particular acrylate groups;
- Examples of particularly suitable starting products (a) for variant (ii) are the adducts of hexamethylene diisocyanate or isophorone diisocyanate with 2-hydroxyethyl acrylate in a molar ratio of 1: 1.
- Examples of suitable starting products (a) for variant (iii) are the reaction products of
- Diisocyanates and compounds containing at least one isocyanate-reactive group and at least one group (a)
- trifunctional compounds which contain at least one, in particular three, isocyanate-reactive grappes, in particular hydroxyl groups,
- reaction products of this type are the reaction products of the adducts of hexamethylene diisocyanate or isophorone diisocyanate with 2-hydroxyethyl acrylate in a 1: 1 molar ratio with trimethylolpropane in a 1: 1 molar ratio.
- suitable starting products (a) for variant (iii) are the reaction products of Triisocyanates, in particular isocyanurates of the diisocyanates described above, with
- reaction products of this type are the reaction products of the isocyanurates of hexamethylene diisocyanate or isophorone diisocyanate with 2-hydroxyethyl acrylate in a molar ratio of 1: 1.
- Variants (i) and (ii) are preferably used with the corresponding starting products (a), variant (i) being preferred. There are further advantages here if the corresponding starting products (a) are already used in the production of the grand structure, which is why this variant is used with particular preference.
- suitable starting products (e) for the introduction of the chemically bound stabilizers (e) are HALS compounds, preferably 2,2,6,6-tetraalky lpiperidine derivatives, in particular 2,2,6,6-tetramethyl lpiperidine derivatives, the nitrogen atom of which contains an oxygen atom , an alkyl group, alkylcarbonyl group or alkyl ether group and which contain an isocyanate group or an isocyanate-reactive functional group (b) or (c), in particular a hydroxyl group.
- An example of a particularly suitable starting product (s) is the nitroxyl radical 2,2,6,6-tetramethyl-4-hydroxy-piperidine-N-oxide.
- Suitable starting products (f) for the introduction of the chemically bound photoinitiators and / or photocoinitiators (f) are those above described photoinitiators and / or photocoinitiators (f) which contain an isocyanate group or an isocyanate-reactive functional group (b) or (c), in particular a hydroxyl group.
- the solid compound (B) can be prepared from the above-described starting products (a) and the starting products for the basic structure and optionally the starting products (b), (c), (e) and / or (f) in a customary and known manner in solution become.
- a further particular advantage of the particularly advantageous solid compounds (B) is that they can be produced in the melt without problems, so that the disposal of organic solvents can be dispensed with.
- the solid compound (B) is amorphous, partially crystalline or crystalline. It is preferably semicrystalline or crystalline, because as a result it is block-resistant and easy to grind even at low molecular weights, in particular in the oligomer range, especially from 500 to 5,000 Daltons, and results in a low-viscosity melt. It is also advantageous if it has a narrow molecular weight distribution because this also has a positive effect on the blocking resistance and the melt viscosity.
- the degree of crystallinity and the molecular weight distribution can be adjusted by customary and known methods, so that the person skilled in the art can carry them out in a simple manner, if necessary with the aid of simple preliminary tests.
- the solid compound (B) preferably has a melting interval or a melting point in the temperature range from 40 to 130 ° C.
- Their melt viscosity at 130 ° C. is preferably 50 to 20,000 Pas.
- the solid compound (B) is preferably in an amount of 5.0 to 95, preferably 10 to 90, particularly preferably 15 to 85, based on the substance mixture according to the invention, contain very particularly preferably 20 to 80 and in particular 25 to 75 wt .-%.
- the mixture of substances according to the invention can be used as an adhesive or sealant or for the production of adhesives and sealants.
- the relevant adhesives and sealants according to the invention then contain at least one additive in effective amounts, as is usually used in the field of hot melt adhesives and sealants.
- the mixture of substances according to the invention is advantageously used as a coating material or for the production of coating materials, preferably solid coating materials and in particular powder coatings.
- the substance mixture according to the invention is preferably present in the powder coating according to the invention in an amount of 50 to 100, preferably 50 to 98, particularly preferably 55 to 95, very particularly preferably 55 to 90% by weight, based in each case on the powder coating according to the invention.
- the powder coatings of the invention based on at least one mixture of substances according to the invention are curable thermally and / or with actinic radiation.
- the combination of thermal curing and curing with actinic radiation is also referred to as dual cure.
- composition of the powder coating materials of the invention can be varied extremely widely, which is a very significant advantage.
- the composition depends on the one hand on the curing method or the curing methods to be used and on the other hand on the intended use of the powder coating (pigment-free clearcoat or pigment-containing color and / or effect coating).
- Suitable further constituents for use in the powder coating materials according to the invention are oligomers and / or polymers which are curable thermally and / or with active radiation and have a glass transition temperature Tg of above 40 ° C., such as thermally curable and / or curable with actinic radiation or branched and / or block-like, comb-like and / or randomly constructed poly (meth) acrylates or acrylate copolymers, polyesters, alkyds, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters or polyureas or other (mem) acrylic functional (meth) acrylate copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates,
- Solid amorphous, semi-crystalline and / or crystalline polyesters are advantageous which contain terminal grapples which are formed from the adduct of dicyclopentadiene and maleic anhydride in a molar ratio of 1: 1 and / or contain endomethylene tetrahydrophthalic acid groups in the chain.
- the production of these polyesters is customary and known and can be carried out using the starting products described above in the production of the polyester polyurethanes.
- powder coatings according to the invention can also contain additives customary in coatings.
- suitable customary additives for use in the powder coatings according to the invention are
- Customary and known reactive diluents curable thermally and / or with actinic radiation such as positionally isomeric diethyloctanediols or hyperbranched compounds containing hydroxyl groups or
- Dendrimers di- or higher functional (meth) acrylates such as Trimethylolpropane tri (meth) acrylate, or (meth) acrylate group-containing polyisocyanates;
- Crosslinking agents which contain the functional groups (b) and / or (c) described above, such as amino resins, compounds or resins containing anhydride groups, compounds or resins containing epoxy groups, tris (alkoxycarbonylamino) triazines, compounds or resins containing carbonate groups, blocked and / or unblocked polyisocyanates, beta-hydroxyalkylamides and compounds with an average of at least two capable of transesterification
- Grapples for example, reaction products of malonic acid diesters and polyisocyanates or of esters and partial esters of polyhydric alcohols of malonic acid with monoisocyanates, as described in European patent EP-A-0 596 460;
- UV absorbers
- Light-treatment agents such as HALS compounds, benzotriazoles or oxalanilides
- 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 benzpinacol silyl ether
- Crosslinking catalysts such as dibutyltin dilaurate,
- Lithium decanoate or zinc octoate Lithium decanoate or zinc octoate
- Deaerators such as diazadicycloundecane or benzoin; chemically unbound photoinitiators such as those of the Norrish II type, the mechanism of which is based on an intramolecular variant of the hydrogen abstraction reactions, as occurs in a variety of ways in photochemical reactions (for example, see here
- Adhesion promoters such as tricyclodecanedimethanol
- Matting agents such as magnesium stearate
- Electrically conductive pigments such as metal pigments, conductivity blacks, doped pearlescent pigments or conductive barium sulfate. Particularly good suitable electrically conductive pigments are the conductivity class; In addition, reference is made to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Metallpigmente", p. 381, and “Leit Pigments", p. 354;
- Effect pigments such as platelet pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE-A-36 36 183 and commercially available stainless steel bronzes, as well as non-metallic effect pigments such as, for example, pearlescent or interference pigments; in addition, Römpp Lexikon Lacke and
- inorganic coloring pigments such as titanium dioxide, iron oxides,
- Sicotrans yellow and carbon black or organic coloring pigments such as thioindigo pigments indanthrene blue, Cromophthahot, Irgazinorange and Heliogengreen; in addition, Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, pages 180 and 181, "Iron Blue Pigments” to "Iron Oxide Black", pages 451 to 453
- organic and inorganic fillers such as chalk, calcium sulfates, barium sulfate, silicates such as talc or kaolin, silicas, oxides such as
- Aluminum hydroxide or magnesium hydroxide or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour;
- suitable paint additives are described in the textbook “Paint Additives” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.
- additives are added to the powder coatings according to the invention in customary and known, effective amounts which, depending on the additive, can range from 0.001 to 500 parts by weight per 100 parts by weight of the solid according to the invention.
- the preparation of the powder coatings according to the invention has no special features in terms of method, but instead is carried out in a customary and known manner, preferably by mixing components (A) and (B) and, if appropriate, at least one of the other components described above in the melt, by extrusion or kneading, and discharging the melt from the mixing unit, solidification of the resulting homogenized mass, comminution of the mass until the desired grain size results, and optionally views of the resulting powder coating according to the invention under conditions under which there is no premature thermal crosslinking and or crosslinking with actinic radiation and / or other damage to individuals Components of the powder coating according to the invention occur, for example, by thermal degradation.
- the application of the powder coating according to the invention also has no special features in terms of method, but instead takes place with the aid of customary and known methods and devices, for example by electrostatic spraying, conditions also being used here under which no premature thermal crosslinking and / or crosslinking with actinic radiation and / or other damage to individual components of the powder coating according to the invention, for example due to thermal degradation.
- the powder slurry lacquer according to the invention can be applied with the aid of methods and devices which are usually used for the application of spray lacquers.
- the powder coating according to the invention and the powder slurry coating according to the invention can be applied in the most varied of layer thicknesses, so that coatings of the most varied thickness, in particular from 10 to 250 ⁇ m, result.
- the thickness of the coatings depends on the intended use of the coatings and can therefore be easily adjusted by a person skilled in the art.
- the hardening of the applied powder coating layers has no special features in terms of method, but rather the customary and known methods and devices are used.
- Curing with actinic radiation can be carried out with electromagnetic radiation such as X-rays, UV radiation, visible light or near IR light (NIR) or with corpuscular radiation such as electron beams.
- electromagnetic radiation such as X-rays, UV radiation, visible light or near IR light (NIR) or with corpuscular radiation such as electron beams.
- the thermal hardening also has no special features in terms of method, but is carried out according to the customary and known methods, such as heating in a forced air oven or irradiation with IR lamps.
- Suitable substrates are all surfaces of objects to be painted, which are accessible to harden the paint layers located thereon using heat and or actinic radiation.
- the powder coating or powder slurry coating according to the invention in particular as a clear coating, is to a high degree suitable for applications in automotive coating, the painting of furniture and industrial coating, including coil coating, container coating and the coating of electrical components.
- industrial painting it is suitable for painting practically all parts for private or industrial use such as radiators, household appliances, small parts made of metal, hub caps, rims or windings of electric motors.
- the clearcoat according to the invention is suitable as a coating for basecoats, preferably in the automotive industry. It is particularly suitable as a clear coat over water-based paints based on polyesters, polyurethane resins and aminoplast resins.
- the metallic substrates used here can have a primer, in particular a cathodically or anodically deposited and thermally hardened electrodeposition coating. If necessary, the electrocoating can also be coated with a stone chip protection primer or a filler.
- plastics such as ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (abbreviated in accordance with DIN 7728T1).
- the plastics to be painted can of course also be polymer blends, modified plastics or fiber-reinforced plastics.
- the plastics typically used in vehicle construction, in particular motor vehicle construction, can also be used.
- non-functionalized and / or non-polar substrate surfaces these can be pretreated in a known manner with a plasma or with flame and / or coated with a hydro primer from a hydro primer before coating.
- the thermal curing can also be carried out before, during or after process step (4) if the coating materials, sealants and adhesives have the appropriate composition.
- the adhesive layers and seals produced from the adhesives and sealants according to the invention have excellent adhesive strength and sealability even over long periods of time, even under extreme climatic conditions.
- the coatings according to the invention produced from the powder coatings and powder slurry coatings according to the invention have an excellent flow and an excellent overall optical impression. They are weather-resistant and do not yellow even in tropical climates. They can therefore be used for numerous indoor and outdoor applications. Therefore, primed and unprimed substrates, in particular bodies of automobiles and commercial vehicles, industrial components, including plastic parts, packaging, coils and electrical components, or furniture that is coated with at least one coating according to the invention, special technical and economic advantages, in particular a long service life, which makes them particularly attractive for users.
- a (meth) acrylate copolymer was prepared by high-temperature polymerization in accordance with the process described in European patent EP-A-0 650 979.
- a mixture of 400 parts by weight of glycidyl methacrylate, 1,100 parts by weight of methyl methacrylate, 400 parts by weight of styrene, 100 parts by weight of n-butyl acrylate and 60 parts by weight of di-tert-butyl peroxide was continuously added to a template from 600 parts by weight of isopropanol at 170 ° C. for one hour added in 150 parts by weight of isopropanol.
- the polymerization was continued for a further 15 minutes, after which the polymerization was terminated by cooling to room temperature.
- the polymer solution was diluted to one and a half times the amount with xylene, filtered and freed of volatile constituents in a thin-film evaporator at 210 ° C. and a pressure of 1 mbar.
- Feed 420.5 g of hexamethylene diisocyanate (2.5 mol) and 1 g of dibutyltin dilaurate.
- Feed 444 g isophorone diisocyanate and 0.8 g dibutyltin dilaurate.
- the solid compounds (B) were characterized with a Physica plate-plate rheometer.
- the solid compound (B) from Preparation Example 6 was used for Examples 8 to 10.
- the solid compound (B) from preparation example 7 was used.
- the powder coatings according to the invention were produced according to the following general instructions:
- the respective powder coating composition was melted in an oil bath at 140 ° C., poured onto an aluminum sheet, ground after solidification and sieved onto a degreased steel sheet, so that an approximately 70 ⁇ m thick coating layer resulted.
- the sieved powder coating layer was melted on a regulated hot plate at 140 ° C. for 5 minutes.
- a mercury vapor lamp with an emission maximum at approx. 360 nm (Hönle LTV 400) was attached at a distance of 30 cm above the heating plate, which was closed with a sliding panel. After the powder coating layer had melted, the sliding shutter was opened and the melt was exposed for 30 seconds. The panel was then closed again and the sheet was removed from the hot plate.
- the powder coating was tested after storage for 24 hours at room temperature.
- Table 3 provides an overview of the quantitative ratios of components (A) and (B), the tests carried out and the results obtained in the process.
- Table 3 Application properties of the powder coatings according to the invention
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)
- Sealing Material Composition (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19947521 | 1999-10-02 | ||
DE19947521A DE19947521A1 (de) | 1999-10-02 | 1999-10-02 | Mit aktinischer Strahlung aktivierbare Bindungen enthaltendes festes Stoffgemisch und seine Verwendung |
PCT/EP2000/009626 WO2001025356A1 (de) | 1999-10-02 | 2000-10-02 | Mit aktinischer strahlung aktivierbare bindungen enthaltendes festes stoffgemisch und seine verwendung |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1218459A1 true EP1218459A1 (de) | 2002-07-03 |
Family
ID=7924296
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00971308A Withdrawn EP1218459A1 (de) | 1999-10-02 | 2000-10-02 | Mit aktinischer strahlung aktivierbare bindungen enthaltendes festes stoffgemisch und seine verwendung |
Country Status (4)
Country | Link |
---|---|
US (1) | US6780897B1 (de) |
EP (1) | EP1218459A1 (de) |
DE (1) | DE19947521A1 (de) |
WO (1) | WO2001025356A1 (de) |
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DE10009822C1 (de) * | 2000-03-01 | 2001-12-06 | Basf Coatings Ag | Verfahren zur Herstellung von Beschichtungen, Klebschichten oder Dichtungen für grundierte oder ungrundierte Substrate und Substrate |
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US20060088720A1 (en) * | 2004-10-22 | 2006-04-27 | Niederst Ken W | Coated packaging materials |
DE102004052874A1 (de) * | 2004-11-02 | 2006-05-04 | Basf Ag | Stabilisierte thermoplastische Formmassen |
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DE102006030059A1 (de) * | 2006-06-29 | 2008-01-17 | Basf Coatings Ag | Verfahren zur Herstellung farb- und/oder effektgebender Mehrschichtlackierungen |
EP1985674A1 (de) * | 2007-04-27 | 2008-10-29 | Cytec Surface Specialties, S.A. | Polymerzusammensetzungen |
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JP5746967B2 (ja) * | 2008-07-11 | 2015-07-08 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | モールド・イン・プレース型ガスケット用、改善されたシール特性を有する組成物 |
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- 1999-10-02 DE DE19947521A patent/DE19947521A1/de not_active Withdrawn
-
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- 2000-02-10 US US10/089,173 patent/US6780897B1/en not_active Expired - Fee Related
- 2000-10-02 EP EP00971308A patent/EP1218459A1/de not_active Withdrawn
- 2000-10-02 WO PCT/EP2000/009626 patent/WO2001025356A1/de active Application Filing
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Also Published As
Publication number | Publication date |
---|---|
WO2001025356A1 (de) | 2001-04-12 |
US6780897B1 (en) | 2004-08-24 |
DE19947521A1 (de) | 2001-04-05 |
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