WO2004069910A1 - Härtbare stoffgemische, verfahren zu ihrer herstellung und ihre verwendung - Google Patents
Härtbare stoffgemische, verfahren zu ihrer herstellung und ihre verwendung Download PDFInfo
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- WO2004069910A1 WO2004069910A1 PCT/EP2004/000180 EP2004000180W WO2004069910A1 WO 2004069910 A1 WO2004069910 A1 WO 2004069910A1 EP 2004000180 W EP2004000180 W EP 2004000180W WO 2004069910 A1 WO2004069910 A1 WO 2004069910A1
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- curable
- substance mixtures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the present invention relates to new curable mixtures.
- the present invention relates to a new method for producing curable mixtures.
- the present invention relates to the use of the new curable substance mixtures and the curable substance mixtures produced by the new method for the production of scratch-resistant, self-supporting foils and scratch-resistant molded parts and as coating materials, adhesives and sealants for the production of scratch-resistant coatings, adhesive layers and seals, in particular as coating materials for the production of transparent, clear, scratch-resistant coatings.
- Curable mixtures of substances which are suitable as coating materials for the production of scratch-resistant coatings are known. As is known, they contain components and nanoparticles curable thermally and / or with actinic radiation (cf. international
- Vehicles especially cars, are used, they must have light stabilizers, especially sterically hindered amines (sterically hindered amines,
- HALS HALS
- the scratch-resistant nanoparticles cause considerable problems due to their inorganic nature, which are particularly noticeable with the broom sealants that are used to produce transparent, clear, scratch-resistant coatings, especially clear coats.
- the broom sealants that are used to produce transparent, clear, scratch-resistant coatings, especially clear coats.
- segregation often occurs, which in the coating materials in question leads to such a high level of turbidity that even complete gelling or coagulation that their use leads to Production of clear coats is no longer possible.
- hydrophilic property is understood to mean the constitutional property of a molecule, a functional group or a particle, to penetrate into the aqueous phase or to remain therein. Accordingly, is under the property
- the state of the art takes the measure to modify the surface of the nanoparticles in a complex manner.
- modified Aerosil® R 812 from Degussa as nanoparticles is proposed in American patent US 5,384,367 A1 or international patent application WO 96/34905 A.
- This product is produced by hydrophobically modifying Aerosil® 300 from Degussa, a hydrophilic, pyrogenic silicon dioxide, with hexamethyldisilazane.
- the clearcoats produced from coating materials known from US Pat. No. 5,384,367 A1 can be overpainted again with the same coating materials. The resulting clearcoats should adhere particularly firmly to the original clearcoats.
- the coating materials known from WO 96/34905 A provide coatings which are scratch-resistant and etch-resistant and have a good overall optical impression.
- HALS light stabilizers used in the known coating materials apparently have no influence on the stability of the coating materials, since all types of HALS (unsubstituted, alkyl-substituted and ether-substituted HALS on the cyclic amino groups) are used without distinction.
- the object of the present invention was to provide new curable substance mixtures which no longer have the disadvantages of the prior art, but which are also stable in storage when using economically producible, unmodified or largely unmodified, hydrophilic nanoparticles and no clouding and no increase in viscosity to complete gelling or coagulation.
- the new curable material mixtures are said to be suitable for the economical production of scratch-resistant, self-supporting foils and scratch-resistant molded parts, and as coating materials, adhesives and sealants for the production of scratch-resistant coatings, adhesive layers and seals, in particular as coating materials for the production of transparent, clear, scratch-resistant coatings.
- the new scratch-resistant, self-supporting foils as well as the scratch-resistant molded parts, coatings, adhesive layers and seals, especially the new transparent, clear, scratch-resistant coatings, should remain scratch-resistant and have an excellent overall appearance (appearance) even after many years of outdoor use.
- the present invention was based on the object of a new process for the preparation of curable substance mixtures To provide, which allows the selection of suitable starting products and the production of curable substance mixtures in a simple manner, the resulting curable substance mixtures for the economical production of scratch-resistant, self-supporting foils and scratch-resistant molded parts and as coating materials, adhesives and sealants for the production of scratch-resistant coatings, adhesive layers and seals, in particular as coating materials for the production of transparent, clear, scratch-resistant coatings.
- the new process for the preparation of curable substance mixtures was found, in which one (1) determines the electrophoretic mobility ⁇ e of inorganic nanoparticles and at least one type of inorganic nanoparticle (B) with an electrophoretic mobility ⁇ e ⁇ -0.5 ( ⁇ m / s) / (V / cm) at a pH of 3 to select 7 and
- the selected nanoparticles (B) are mixed with at least one light stabilizer (C) based on sterically hindered amines (HALS) with a pKe value of at least 9.0 and at least one component (A) curable thermally and / or with actinic radiation ,
- HALS sterically hindered amines
- the substance mixtures according to the invention no longer had the disadvantages of the prior art, but were also storage-stable when using economically producible, unmodified or largely unmodified, hydrophilic nanoparticles and no longer exhibited gelling or coagulation. In fact, there were no cloudiness and none Increase in viscosity to be observed.
- the mixtures of substances according to the invention were outstandingly suitable for the economical production of scratch-resistant, self-supporting films and scratch-resistant molded parts, and as coating materials, adhesives and sealants for the economical production of scratch-resistant coatings, adhesive layers and seals, in particular as coating materials for the production of transparent, clear, scratch-resistant coatings.
- the process according to the invention made it possible in a simple manner to select suitable essential starting products and to produce mixtures of substances according to the invention, the resulting mixtures of substances according to the invention for the economical production of scratch-resistant, self-supporting films and scratch-resistant moldings and as coating materials, adhesives and sealants for the production of scratch-resistant coatings , Adhesive layers and seals, particularly as coating materials for the production of transparent, clear, scratch-resistant coatings, were outstandingly suitable.
- the substance mixtures according to the invention contain at least one, in particular at least two, constituent (s) (A) ' from the group consisting of physical, thermal, with actinic radiation and substances curable thermally and with actinic radiation.
- the term “physical hardening” means the hardening of a layer of a hardenable substance mixture by filming by solvent release from the hardenable substance mixture, the connection within the layer via loop formation of the polymer molecules of the binders (for the term see Römpp Lexikon Lacke and printing inks, 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, “Hardening", pages 274 and 275. Usually no crosslinking agents are required for this purpose. If necessary, physical hardening can be supported by atmospheric oxygen, heat or by exposure to actinic radiation.
- the thermally curable constituents (A) in turn can be self-crosslinking or externally crosslinking.
- self-crosslinking denotes the property of a component (A), in particular a binder (A), to undergo crosslinking reactions with itself.
- a prerequisite for this is that at least two types of complementary components already exist in component (A) Reactive functional groups are required which are necessary for crosslinking, whereas curable substance mixtures are referred to as external crosslinking, in which at least one type of complementary reactive functional group is contained in a first constituent (A), in particular a binder (A), and at least one another type in a second component (A), in particular a hardener or crosslinking agent (A).
- external crosslinking in which at least one type of complementary reactive functional group is contained in a first constituent (A), in particular a binder (A), and at least one another type in a second component (A), in particular a hardener or crosslinking agent (A).
- electromagnetic radiation such as near infrared (NIR), visible light, UV radiation, X-rays and gamma radiation, in particular UV radiation, and corpuscular radiation such as electron radiation, beta radiation, alpha radiation and neutron radiation, in particular electron radiation, are included under actinic radiation understand.
- NIR near infrared
- UV radiation visible light
- UV radiation UV radiation
- X-rays and gamma radiation in particular UV radiation
- corpuscular radiation such as electron radiation, beta radiation, alpha radiation and neutron radiation, in particular electron radiation
- the substance mixtures according to the invention preferably contain at least one binder (A).
- the binders (A) are oligomeric and polymeric resins.
- the binders (A) are preferably selected from the group consisting of random, alternating and / or block-like, linear and / or branched and / or comb-like polyaddition resins, polycondensation resins and (co) polymers of ethylenically unsaturated monomers. These terms are supplemented by Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition” and “Polyadditionharze (polyadducts)", and pages 463 and 464, "Polycondensates”, “Polycondensation” and “Polycondensation Resins” and pages 73 and 74, "Binders". Examples of suitable (co) polymers (A) are
- suitable polyaddition resins and polycondensation resins (A) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, in particular polyester polyurethanes.
- the (meth) acrylate (co) polymers (A) have advantages and are therefore used with preference.
- the self-crosslinking binders (A) of the thermally curable substance mixtures and dual-cure substance mixtures according to the invention contain reactive functional groups which can undergo crosslinking reactions with groups of their type or with complementary reactive functional groups.
- the externally crosslinking binders (A) contain reactive functional groups which can undergo crosslinking reactions with complementary reactive functional groups which are present in crosslinking agents (A). Examples of suitable complementary reactive functional groups to be used according to the invention are summarized in the following overview.
- 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 identical or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.
- Binder fA and crosslinking agent (A) or
- Crosslinking agent (A) and binder (A) are crosslinking agent (A) and binder (A)
- the selection of the respective complementary groups is based on the one hand on the fact that they do not undergo any undesired reactions, in particular no premature crosslinking, during the production, storage and application and, if appropriate, during the melting of the substance mixtures according to the invention and / or if necessary curing with actinic radiation must not disturb or inhibit, and on the other hand according to the temperature range in which the crosslinking should take place.
- crosslinking temperatures of the thermally curable or dual-cure curable material mixtures according to the invention crosslinking temperatures of
- the binders (A) contain, in particular, methylol, methylol ether and / or N-alkoxymethylamino groups.
- the functionality of the binders (A) 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 (A) used in each case.
- the acid number is preferably included 10 to 100, preferably 15 to 80, particularly preferably 20 to 75, very particularly preferably 25 to 70 and in particular 30 to 65 mg KOH / g.
- the OH number is preferably 15 to 300, preferably 20 to 250, particularly preferably 25 to 200, very particularly preferably 30 to 150 and in particular 35 to 120 mg KOH / g.
- the epoxy equivalent weight is preferably 400 to 2,500, preferably 420 to 2,200, particularly preferably 430 to 2,100, very particularly preferably 440 to 2,000 and in particular 440 to 1,900 equivalent / g.
- the binders (A) containing hydroxyl groups preferably contain a minor amount of carboxyl groups, preferably corresponding to an acid number ⁇ 30, preferably ⁇ 25 and in particular ⁇ 20 mg KOH / g
- the complementary reactive functional groups described above can be incorporated into the binders (A) by the customary and known methods of 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 mixed with the acid is esterified, 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, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid,
- Hydroxycycloalkyl esters such as 1, 4-
- 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, N, N-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;
- (a3) monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid,
- suitable monomer units for introducing reactive functional groups into polyester or polyester-polyurethane (A) are 2,2-dimethylolethyl- or propylamine, which are blocked with a ketone, the resulting ketoxime group being hydrolyzed again after incorporation; or compounds which have 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 contain at least one sulfonic acid group, such as
- Dimethylolbutyric acid 2,2-dimenthylolpentanoic acid, alpha.omega-diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid or 2,4-diamino-diphenylether sulfonic acid.
- the binders (A) of the dual-cure substance mixtures according to the invention or of the substance mixtures according to the invention curable purely with actinic radiation furthermore contain on average at least one, preferably at least two, group (s) with at least one bond 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 polymerization 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 and carbon-carbon triple 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 which can be activated with actinic radiation, 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 the group in question here. According to the invention, it is particularly advantageous to use two, in particular one, double bond.
- the dual-cure binder (A) or the binder (A) curable purely with actinic radiation contains on average at least one of the groups described above which can be activated with actinic radiation.
- the functionality of the binder in this respect 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 is chosen depends on the requirements placed on the respective dual-cure substance mixtures according to the invention or the substance mixtures according to the invention curable with actinic radiation.
- the groups are structurally different from one another or of the same structure. If they are structurally different from one another, this means within the scope of the present invention that two, three, four or more, but in particular two, groups which can be activated with actinic radiation and which differ from two, three, four or more, in particular two, are used. Derive monomer classes.
- 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 in particular via
- Isocyanates such as vinyl isocyanate, methacryloyl isocyanate and / or 1- (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI® from CYTEC) or isocyanate groups with the above-described monomers containing hydroxyl groups.
- binders (A) which are purely thermally curable and curable purely with actinic radiation can also be used.
- the material composition of the binders (A) basically has no peculiarities, but comes
- EP 0 652 264 A1 described binders intended for use in powder clearcoat slurries curable thermally or thermally and with actinic radiation
- (Meth) acrylate copolymers (A) are used.
- the additional binders (A) for the dual-cure substance mixtures according to the invention or as the sole binders (A) for the substance mixtures according to the invention that are curable purely with actinic radiation are those described in European patent applications EP 0 928 800 A1, EP 0 636 669 A1 , EP 0 410 242 A1, EP 0 783 534 A1, EP 0 650 978 A1, EP 0 650 979 A1, EP 0 650 985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1 or EP 0 002 866 A1, the German patent applications DE 198 35 206 A1, DE 197 09 467 A1, DE 42 03 278 A1, DE 33 16 593 A1, DE 38 36 370 A.
- the preparation of the binders (A)) also has no special features in terms of method, but instead takes place with the aid of the customary and known methods of polymer chemistry, as described in detail, for example, in the patent applications and patents listed above.
- 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, Issue 9, 1995, pages 1409 to 1416.
- polyesters and alkyd resins are described, for example, in the standard work Ulimanns Encyklopadie der Technische Chemie, 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 Alkydes-Polyesters” 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, described.
- polyurethanes and / or acrylated polyurethanes (A) is described, for example, in patent applications EP 0 708 788 A1, DE 44 01 544 A1 or DE 195 34 361 A1.
- the content of binders (A) in the substance mixtures according to the invention can vary very widely and depends primarily on whether they are physically curable, thermally self-crosslinking curable and / or curable with actinic radiation.
- the content can preferably be 20 to 99.9, preferably 25 to 99.7, particularly preferably 30 to 99.5, very particularly preferably 35 to 99.3 and in particular 40 to 99.1% by weight, in each case based on the solids of the mixtures according to the invention.
- the binder content is preferably 10 to 80, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 30 to 60% by weight, in each case based on the solid of the substance mixtures according to the invention.
- the thermally or thermally and with actinic radiation curable, crosslinking substance mixtures contain at least one crosslinking agent (A) which contains the reactive functional groups complementary to the reactive functional groups of the binders (A).
- A crosslinking agent
- the person skilled in the art can therefore easily select the crosslinking agents (A) suitable for a given powder slurry.
- beta-hydroxyalkylamides such as N, N, N ', N'-T ⁇ trakis (2-hydroxyethyl) adipamide or N, N, N', N , -Tetrakis (2-hydroxypropyl) - adipamide and / or
- Tris (alkxycarbonylamino) triazines are preferably used.
- the content of the crosslinking agents (A) in the substance mixtures according to the invention can likewise vary very widely and depends on the requirements of the individual case, in particular on the number of reactive functional groups present. It is preferably 1.0 to 50, preferably 2.0 to 45, particularly preferably 3.0 to 40, very particularly preferably 4.0 to 35 and in particular 5.0 to 30% by weight, in each case based on solids mixtures of substances according to the invention.
- the substance mixtures according to the invention contain at least one, in particular one, type of inorganic nanoparticles (B) with an electrophoretic mobility ⁇ e ⁇ - 0.5, preferably ⁇ - 1 and in particular ⁇ - 1.5 ( ⁇ m / s) / (V / cm) at a pH of 3 to 7.
- the electrophoretic mobility can be determined with the aid of laser Doppler electrophoresis.
- the Zetasizer ® 3000 from Malvern can be used as the measuring device. However, microelectrophoretic (microscopic) measurement methods can also be used.
- the nanoparticles (B) are preferably selected from the group consisting of main and subgroup metals and their compounds.
- the main and subgroup metals are preferably selected from metals of the third to fifth main group, the third to sixth and the first and second subgroups of the periodic table of the elements and the lanthanides.
- the compounds of the metals are preferably the oxides, oxide hydrates, sulfates or phosphates, in particular oxides.
- pyrogenic silicon dioxide is pyrogenic silicon dioxide.
- the agglomerates and aggregates of its primary particles have a chain structure and are produced by flame hydrolysis of silicon tetrachloride in a detonating gas flame.
- the pyrogenic silicon dioxide as such is hydrophilic and can be used without further notice Modification or after only a minor modification of its surface can be used as nanoparticles (B).
- “Minor” means that when the surface is modified, only a small part, in particular ⁇ 50 equivalent%, of the silanol groups present on the surface of the nanoparticles are reacted with customary and known modifiers.
- the nanoparticles (B) to be modified preferably have a primary particle size ⁇ 50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm.
- the content of the substance mixtures according to the invention in the nanoparticles (B) to be used according to the invention described above can vary very widely and depends on the requirements of the individual case.
- the content is preferably 0.1 to 40, preferably 0.5 to 35, particularly preferably 1.0 to 40, very particularly preferably 1.5 to 35 and in particular 2.0 to 30% by weight, in each case based on the Solids of the mixtures according to the invention.
- the substance mixtures according to the invention further contain at least one, in particular one, light stabilizer (C) based on sterically hindered amines (HALS) with a pKe value of at least 9.0, in particular at least 9.5.
- the light stabilizers (C) are preferably selected from the group of aminoether-functionalized HALS.
- the amino ether functionalized 2,2,6,6-tetramethylpiperidine derivatives are used, such as bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, which is available from Ciba Specialty Chemicals under the brand name Tinuvin ⁇ 123 is distributed.
- aminoether-functionalized HALS which have at least one reactive molecule which is complementary to the reactive functional groups of the crosslinking agent and / or binder (A) contain functional group so that they are immobilized during the thermal crosslinking of the substance mixtures according to the invention.
- the substance mixtures according to the invention preferably contain the light stabilizers (C) in an amount of 0.1 to 5, preferably 0.2 to 4 and in particular 0.3 to 3% by weight, based in each case on the solids of the substance mixtures according to the invention.
- the mixtures of substances according to the invention can further contain at least one additive (D).
- additives are preferably selected from the group consisting of photoinitiators; molecularly dispersible dyes; low and high boiling ("long") organic solvents; Venting means; Wetting agents; emulsifiers; Slip additives polymerization inhibitors; Catalysts for the thermal crosslinking of thermolabile free radical initiators; Adhesion promoters; Leveling agents film-forming aids; Rheology aids such as thickeners and pseudoplastic Sag control agents, SCA; Triazine and benzotriazole based light stabilizers; Flame retardants; Corrosion inhibitors; anti-caking agents; To grow; driers; Biocides and matting agents.
- the substance mixtures according to the invention which contain the additives (D) described above, are used for the production of clear, transparent, hardened substance mixtures, in particular for the production of clear, transparent coatings, adhesive layers, seals, films and moldings.
- the mixtures of substances according to the invention can, however, also be pigmented. They then preferably contain, as an additive or as one of the additives (D), at least one customary and known pigment selected from the group consisting of organic and inorganic, transparent and opaque, color and / or effect, electrically conductive, magnetically shielding and fluorescent Pigments and fillers.
- the pigmented substance mixtures according to the invention are used in particular as coating materials, such as electrical smoke coatings, fillers, basecoats and solid-color topcoats, for the production of pigmented coatings, such as electrical smoke coatings, filler coatings or stone chip protection primers, basecoats and
- Solid color finishes or used to manufacture pigmented adhesive layers, seals, foils and molded parts.
- the pigmented substance mixtures according to the invention can also be used for the production of pigmented, transparent hardened substance mixtures, in particular of transparent coatings, adhesive layers, seals, foils and molded parts.
- the substance mixtures according to the invention are preferably produced by mixing the constituents described above in suitable mixing units such as stirred kettles, agitator mills, extruders, kneaders, Ultraturrax, in-line dissolvers, static mixers, micromixers, gear rim dispersers,
- Pressure relief nozzles and / or microfluidizers Preference is given to excluding light of a wavelength ⁇ ⁇ 550 nm or to completely excluding light in order to prevent premature crosslinking of the compositions according to the invention if the compositions according to the invention are curable with actinic radiation or with dual-cure.
- customary and known temporary or permanent substrates are preferably used for the production of the films and molded parts according to the invention, such as metal and plastic strips or hollow bodies made of metal, glass, plastic, wood or ceramic, which can be easily removed without damaging the films and molded parts according to the invention ,
- the substance mixtures according to the invention are used for the production of coatings, adhesive layers, primers and seals, permanent substrates are used, such as means of transportation, including aircraft, watercraft, rail vehicles, muscle-powered vehicles and motor vehicles, and parts thereof, structures indoors and outdoors and Parts thereof, doors, windows, furniture, hollow glass bodies, coils, containers, packaging, small industrial parts, optical components, electrotechnical components, mechanical components and components for white would.
- the films and moldings according to the invention can also serve as substrates.
- the application of the liquid substance mixtures according to the invention has no peculiarities, but can be done by all customary and known application methods, such as Spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling.
- the application of the powdery mixtures of substances according to the invention has no special features in terms of method, but is carried out, for example, using the customary and known fluidized bed processes, such as those found in the company publications from BASF Coatings AG, “Powder coatings for industrial applications”, January 2000, or “Coatings Partner, powder coating Spezial «, 1/2000, or Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 187 and 188,» Electrostatic Powder Spraying «,» Electrostatic Spraying «and» Electrostatic Whirl Bath Process «.
- compositions according to the invention are curable with actinic radiation or with dual-cure.
- the applied substance mixtures according to the invention are preferably cured with UV radiation.
- a radiation dose of 100 to 6,000, preferably 200 to 3,000, preferably 300 to 2,000 is preferred for the irradiation and particularly preferably 500 to 1,800 mJcm "2 are used, the range ⁇ 1,700 mJcm " 2 being very particularly preferred.
- the radiation intensity can vary widely. It depends in particular on the radiation dose on the one hand and the radiation duration on the other. For a given radiation dose, the irradiation time depends on the belt or feed speed of the substrates in the irradiation system and vice versa.
- UV lamps can be used as radiation sources for the UV radiation. Flash lamps can also be used.
- Mercury vapor lamps preferably mercury low, medium and high pressure vapor lamps, are preferred as UV lamps, in particular
- Unmodified mercury vapor lamps plus suitable filters or modified, in particular doped, mercury vapor lamps are particularly preferably used.
- Gallium-doped and / or iron-doped, in particular iron-doped, mercury vapor lamps are preferably used, as described, for example, in R. Stephen Davidson, "Exploring the Science, Technology and Applications of UN. and E.B. Curing «, Sita Technology Ltd., London, 1999, Chapter I,» An Overview «, page 16, Figure 10, or Dipl.-Ing. Peter Klamann, “eltosch system competence, UV technology, guidelines for users”, page 2, October 1998.
- Suitable flash lamps are flash lamps from VISIT.
- the distance of the UV lamps from the applied compositions according to the invention can vary surprisingly widely and therefore very well on the The requirements of the individual case can be set.
- the distance is preferably 2 to 200, preferably 5 to 100, particularly preferably 10 to 50 and in particular 15 to 30 cm.
- Their arrangement can also be adapted to the conditions of the substrate and the process parameters.
- the areas which are not accessible to direct radiation (shadow areas), such as cavities, folds and other design-related undercuts can be combined with point, small area or all-round emitters, combined with an automatic movement device for the irradiation of Cavities or edges, are cured.
- the irradiation can be carried out under an oxygen-depleted atmosphere.
- Oxygen-depleted means that the content of oxygen in the atmosphere is lower than the oxygen content of air (20.95% by volume).
- the atmosphere can basically also be oxygen-free, ie it is an inert gas. Because of the lack of However, the inhibiting effect of oxygen can cause a strong acceleration of radiation curing, which can result in inhomogeneities and stresses in the hardened compositions according to the invention. It is therefore advantageous not to reduce the oxygen content of the atmosphere to zero% by volume.
- the thermal curing can be carried out, for example, with the aid of a gaseous, liquid and / or solid, hot medium, such as hot air, heated oil or heated rollers, or with the aid of microwave radiation , Infrared light and / or near infrared light (NIR).
- the heating is preferably carried out in a forced air oven or by irradiation with IR and / or NIR lamps.
- thermal curing can also be used done gradually. The thermal curing advantageously takes place at temperatures from room temperature to 200.degree.
- Both thermal curing and curing with actinic radiation can be carried out in stages. They can take place one after the other (sequentially) or simultaneously. Sequential curing is advantageous according to the invention and is therefore used with preference. It is particularly advantageous to carry out the thermal hardening after the hardening with actinic radiation.
- the resulting films, moldings, coatings, adhesive layers and seals according to the invention are outstandingly suitable for coating, gluing, sealing, wrapping and packaging of means of transportation, including aircraft, watercraft, rail vehicles, muscle-powered vehicles and motor vehicles, and parts thereof, structures inside - and outdoor areas and parts thereof, doors, windows and furniture as well as in the context of industrial painting of hollow glass bodies, coils, containers, packaging, small industrial parts such as nuts, screws or hubcaps, optical components, electrical components, such as winding materials, including coils and stators and rotors for electric motors, mechanical components and components for white goods, including household appliances, boilers and radiators.
- the substance mixtures according to the invention are used as coating materials for the production of clear, transparent coatings, preferably clearcoats, preferably clearcoats of color and / or effect-giving, electrically conductive, magnetically shielding or fluorescent multi-layer coatings, particularly preferably of clearcoats of color and / or or effect-giving multi-layer coatings and in particular of clear coats of coloring and / or effect-giving multi-coat coats which have the so-called automotive quality (cf. also European patent EP 0 352 298 B1, page 15, line 42, to page 17, line 40).
- the multicoat paint systems according to the invention are preferably applied by the customary and known wet-on-wet processes (see, for example, German patent applications DE 199 14 896 A1, column 16, line 54 to column 18, line 57, or DE 199 30 067 A1) , Page 15, line 25, to page 16, line 36).
- the resulting coatings, moldings and films according to the invention are simple to produce and have excellent optical properties (appearance) and very high resistance to light, chemicals, water, condensation, weather and etching , In particular, they are free from cloudiness and inhomogeneities. They have excellent scratch resistance and abrasion resistance with excellent surface hardness and acid resistance.
- the coatings, in particular the clearcoats only experience a difference in gloss before and after exposure to less than 30, preferably less than 27 and in particular less than 25 units, which underpins their particularly high scratch resistance.
- the adhesive layers according to the invention permanently bond a wide variety of substrates to one another and have high chemical and mechanical stability even in the case of extreme temperatures and / or temperature fluctuations.
- the seals according to the invention permanently seal the substrates, and they also have high chemical and mechanical stability even in the case of extreme temperatures and / or temperature fluctuations. V. m. exposed to aggressive chemicals.
- the primed or unprimed substrates usually used in the above-mentioned technological fields which are coated with at least one coating according to the invention, bonded with at least one adhesive layer according to the invention, sealed with at least one seal according to the invention and / or with at least one film according to the invention or at least one molding according to the invention are wrapped or packaged, with a particularly advantageous application-related property profile, a particularly long service life, which makes them economically and ecologically particularly attractive.
- Reflux coolers were weighed in 897 g of a fraction of aromatic hydrocarbons with a boiling range of 158-172 ° C.
- the solvent was heated to 140 ° C.
- a monomer mixture of 487 g of t-butyl acrylate, 215 g of n-butyl methacrylate, 143 g of styrene, 572 g of hydroxypropyl methacrylate and 14 g of acrylic acid were added within 4 hours, and an initiator solution of 86 g of t Butyl perethylhexanoate in 86 g of the aromatic solvent described is metered uniformly into the reactor within 4.5 hours.
- the metering of the monomer mixture and the initiator solution was started simultaneously. After the initiator metering had ended, the reaction mixture was kept at 140 ° C. for a further two hours and then cooled.
- the resulting polymer solution diluted with a mixture of 1-methoxypropylacetate-2, butylglycol acetate and butyl acetate, had a solids content of 53%, determined in a forced air oven at 130 ° C. for 1 h, an acid number of 10 mg KOH / g and a viscosity of 23 dPas ( measured on a 60% solution of the polymer solution in the aromatic solvent described, using an ICI plate-cone viscometer at 23 ° C).
- a monomer mixture of 537 g of 2-ethyl-hexyl methacrylate, 180 g of n-butyl methacrylate, 210 g of styrene, 543 g of hydroxyethyl acrylate and 30 g of acrylic acid were added within 4 hours, and an initiator solution of 150 g of t-butyl perethyl hexanoate 90 g of the aromatic solvent described are metered uniformly into the reactor over the course of 4.5 hours.
- the metering of the monomer mixture and the initiator solution was started simultaneously. After the end of the initiator metering, the reaction mixture is held at 140 ° C. for a further two hours then cooled.
- the resulting polymer solution had a solids content of 65%, determined in a forced-air oven for 1 h at 130 ° C., an acid number of 17 mg KOH / g and a viscosity of 16 dPas (measured on a 60% solution of the polymer solution in the aromatic solvent described , using an ICI plate-cone viscometer at 23 ° C).
- a monomer mixture of 450 g of 2-ethyl-hexyl methacrylate, 180 g of n-butyl methacrylate, 210 g of styrene, 180 g of hydroxyethyl acrylate, 450 g of 4-hydroxybutyl acrylate and 30 g of acrylic acid were added within 4 hours, and an initiator solution of 150 g of t-butyl perethylhexanoate in 90 g of the aromatic solvent described are metered uniformly into the reactor over the course of 4.5 hours.
- the metering of the monomer mixture and the initiator solution was started simultaneously. After the initiator metering had ended, the reaction mixture was kept at 140 ° C.
- the clear coats 1 (examples 1) and V 1 (comparative test V 1) were prepared by mixing the constituents given in table 1 and homogenizing the respective mixtures.
- Binder solution (A 1) according to preparation example 1 31, 32 31, 32
- Binder solution (A 2) according to preparation example 2 8.0 8.0
- TACT ® (commercial tris (alkoxycarbonylamino) triazine from Cytec) 21, 0 21, 0
- Baysilon ® OL 44 (commercially available leveling agent based on a modified polysiloxane from
- Highlink ® OG 502-31 (dispersion of unmodified silicon dioxide nanoparticles a) , 30 percent in isopropanol, from Clariant) 30.5 30.5
- Example 1 The clear coat 1 of Example 1 was clear and completely free from cloudiness even after storage for 24 hours. Its discharge viscosity at 23 ° C in the DIN 4 discharge cup remained constant at 16 seconds. It was ideal for the production of clear coats. In contrast, the clear lacquer V 1 of the comparative test V 1 was cloudy after 24 hours of storage and gelled so strongly that its leakage viscosity was no longer measurable; it was no longer suitable for an application.
- the clear coats 2 and 3 were produced by mixing the constituents listed in Table 2 and homogenizing the respective mixtures.
- Table 2 The material composition of Kiarlacke 2 and 3
- Binder solution (A 1) according to Preparation Example 1 36.137 30.047
- Baysilon ® OL 44 (commercially available leveling agent based on a modified polysiloxane from Bayer AG) 0.063
- Tinuvin ® 400 (commercially available light stabilizer based on triazine from Ciba Specialty Chemicals) 1.1 0.9 Highlink ® OG 502-31 (dispersion of unmodified
- Silicon dioxide nanoparticles 30 percent in
- the clear coats 2 and 3 were stable on storage and showed no turbidity and no increase in viscosity even after storage for several weeks. They were ideal for the production of clear coats.
- steel panels were coated in succession with a cathodic electrodeposition coating which had been baked at 170 ° C. for 20 minutes and had a dry layer thickness of 18 to 22 ⁇ m.
- the steel panels were then coated with a commercially available two-component water filler from BASF Coatings AG.
- the resulting filler layer was baked at 90 ° C. for 30 minutes, so that a dry layer thickness of 35 to 40 ⁇ m resulted.
- the commercially available water-based lacquer "Starsilber" from BASF Coatings AG was applied with wet layer thicknesses, which resulted in dry layer thicknesses of 12 to 15 ⁇ m after curing, after which the resulting water-based lacquer layers were flashed off at 80 ° C. for ten minutes.
- the clear coats 2 and 3 were applied pneumatically in a cloister with a gravity cup gun oil.
- the wet layer thicknesses of the clear lacquer layers were set in such a way that dry layer thicknesses of 40 to 45 ⁇ m each resulted after curing.
- the water-based lacquer layers and the clear lacquer layers were cured for 5 minutes at room temperature, for 10 minutes at 80 ° C. and finally for 20 minutes at 140 ° C. The result was the multi-layer paintwork 4 and 5.
- micro penetration hardness was determined as universal hardness at 25.6 mN using a Fischerscope 100V with a diamond pyramid according to Vickers.
- the chemical resistance was determined according to BART (BASF ACID RESISTANCE TEST).
- the multicoat paint systems 4 and 5 were exposed to temperature loads on a gradient oven (30 min, 50 ° C, 60 ° C and 70 ° C and 80 ° C).
- the test substances sulfuric acid 1%, 10%, 36%; sulfuric acid 5%, hydrochloric acid 10%, sodium hydroxide solution 5%, demineralized water - 1, 2, 3 or 4 drops
- Table 3 Hardness, scratch resistance, condensation resistance and acid resistance of the multi-layer coatings 4 and 5
- Gloss before mechanical stress 85.2 80.3 Gloss difference after mechanical stress 2.3 1.1 Gloss difference after reflow (2 h / 40 ° C) - 0.7 0.9 Gloss difference after reflow (2 h / 80 ° C) - 0.8 1.0
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP04701915A EP1590399A1 (de) | 2003-02-03 | 2004-01-14 | Härtbare stoffgemische, verfahren zu ihrer herstellung und ihre verwendung |
US10/542,207 US20060148944A1 (en) | 2003-02-03 | 2004-01-14 | Hardenable mixtures, method for the production thereof, and use of the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10304127A DE10304127A1 (de) | 2003-02-03 | 2003-02-03 | Härtbare Stoffgemische, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10304127.3 | 2003-02-03 |
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WO2004069910A1 true WO2004069910A1 (de) | 2004-08-19 |
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ID=32695136
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PCT/EP2004/000180 WO2004069910A1 (de) | 2003-02-03 | 2004-01-14 | Härtbare stoffgemische, verfahren zu ihrer herstellung und ihre verwendung |
Country Status (4)
Country | Link |
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US (1) | US20060148944A1 (de) |
EP (1) | EP1590399A1 (de) |
DE (1) | DE10304127A1 (de) |
WO (1) | WO2004069910A1 (de) |
Families Citing this family (7)
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DE10344449A1 (de) * | 2003-09-25 | 2005-04-28 | Henkel Kgaa | Klebstoff-Zusammensetzung mit Barriere-Eigenschaften |
US7531595B2 (en) * | 2006-03-08 | 2009-05-12 | 3M Innovative Properties Company | Pressure-sensitive adhesive containing silica nanoparticles |
US7645827B2 (en) * | 2006-03-08 | 2010-01-12 | 3M Innovative Properties Company | High shear pressure-sensitive adhesive |
DE102006044310A1 (de) * | 2006-09-18 | 2008-03-27 | Nano-X Gmbh | Silanbeschichtungsmaterial und Verfahren zur Herstellung eines Silanbeschichtungsmaterials |
US20080200587A1 (en) * | 2007-02-16 | 2008-08-21 | 3M Innovative Properties Company | Pressure-sensitive adhesive containing acicular silica particles crosslinked with polyfunctional aziridines |
US9150701B2 (en) * | 2007-12-21 | 2015-10-06 | Basf Se | Nano structured UV absorbers |
DE102008029723B3 (de) * | 2008-06-24 | 2009-11-12 | Flooring Technologies Ltd. | Verfahren zur Herstellung von Holzwerkstoffplatten mit kratzfesten Oberflächen |
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EP0555052A1 (de) * | 1992-02-03 | 1993-08-11 | General Electric Company | Abriebfeste Überzugszusammensetzungen |
EP0576247A2 (de) * | 1992-06-25 | 1993-12-29 | General Electric Company | Strahlungshärtbare Hartüberzugszusammensetzungen |
JPH08209028A (ja) * | 1995-04-27 | 1996-08-13 | Mitsubishi Rayon Co Ltd | 被覆用組成物、それを用いた表面被覆成形物 |
US5811472A (en) * | 1996-07-22 | 1998-09-22 | General Electric Company | Radiation curable compositions having improved moisture resistance |
US6265061B1 (en) * | 1998-05-04 | 2001-07-24 | 3M Innovative Properties Company | Retroflective articles including a cured ceramer composite coating having abrasion and stain resistant characteristics |
US20030045598A1 (en) * | 2001-07-31 | 2003-03-06 | General Electric Company | Radiation curable coating compositions |
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US5384367A (en) * | 1993-04-19 | 1995-01-24 | Ppg Industries, Inc. | Carbamate urea or urethane-functional epoxy acrylic with polyacid |
DE19811790A1 (de) * | 1998-03-18 | 1999-09-23 | Bayer Ag | Nanopartikel enthaltende transparente Lackbindemittel mit verbesserter Verkratzungsbeständigkeit, ein Verfahren zur Herstellung sowie deren Verwendung |
DE19920799A1 (de) * | 1999-05-06 | 2000-11-16 | Basf Coatings Ag | Thermisch und mit aktinischer Strahlung härtbarer Beschichtungsstoff und seine Verwendung |
DE19947523A1 (de) * | 1999-10-02 | 2001-04-05 | Basf Coatings Ag | Feststoff, enthaltend über Urethangruppen an die Grundstruktur gebundene Gruppen, die mit aktinischer Strahlung aktivierbare Bindungen enthalten, und ihre Verwendung |
DE10129899A1 (de) * | 2001-06-21 | 2003-01-09 | Basf Coatings Ag | Physikalisch, thermisch oder thermisch und mit aktinischer Strahlung härtbarer wäßriger Beschichtungsstoff und seine Verwendung |
-
2003
- 2003-02-03 DE DE10304127A patent/DE10304127A1/de not_active Ceased
-
2004
- 2004-01-14 US US10/542,207 patent/US20060148944A1/en not_active Abandoned
- 2004-01-14 WO PCT/EP2004/000180 patent/WO2004069910A1/de not_active Application Discontinuation
- 2004-01-14 EP EP04701915A patent/EP1590399A1/de not_active Withdrawn
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EP0555052A1 (de) * | 1992-02-03 | 1993-08-11 | General Electric Company | Abriebfeste Überzugszusammensetzungen |
EP0576247A2 (de) * | 1992-06-25 | 1993-12-29 | General Electric Company | Strahlungshärtbare Hartüberzugszusammensetzungen |
JPH08209028A (ja) * | 1995-04-27 | 1996-08-13 | Mitsubishi Rayon Co Ltd | 被覆用組成物、それを用いた表面被覆成形物 |
US5811472A (en) * | 1996-07-22 | 1998-09-22 | General Electric Company | Radiation curable compositions having improved moisture resistance |
US6265061B1 (en) * | 1998-05-04 | 2001-07-24 | 3M Innovative Properties Company | Retroflective articles including a cured ceramer composite coating having abrasion and stain resistant characteristics |
US20030045598A1 (en) * | 2001-07-31 | 2003-03-06 | General Electric Company | Radiation curable coating compositions |
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DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 7 November 1996 (1996-11-07), WATANABE, HIROYUKI ET AL WATANABE, HIROYUKI ET AL: "Abrasion- and weather-resistant coating materials and their use of surface-coated moldings Abrasion- and weather-resistant coating materials and their use of surface-coated moldings", XP002283711, retrieved from STN Database accession no. 1996:658666 * |
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US20060148944A1 (en) | 2006-07-06 |
EP1590399A1 (de) | 2005-11-02 |
DE10304127A1 (de) | 2004-08-12 |
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