EP1945377A1 - Films pour reparation et leur utilisation - Google Patents

Films pour reparation et leur utilisation

Info

Publication number
EP1945377A1
EP1945377A1 EP06840929A EP06840929A EP1945377A1 EP 1945377 A1 EP1945377 A1 EP 1945377A1 EP 06840929 A EP06840929 A EP 06840929A EP 06840929 A EP06840929 A EP 06840929A EP 1945377 A1 EP1945377 A1 EP 1945377A1
Authority
EP
European Patent Office
Prior art keywords
repair
layer
temporary carrier
carrier film
films according
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.)
Withdrawn
Application number
EP06840929A
Other languages
German (de)
English (en)
Inventor
Hubert Baumgart
Berthold Austrup
Bostjan Muhic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1945377A1 publication Critical patent/EP1945377A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B05D1/286—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers using a temporary backing to which the coating has been applied
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/005—Repairing damaged coatings
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • 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
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • 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
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2848—Three or more layers
    • 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]
    • Y10T428/31507—Of polycarbonate
    • 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]
    • Y10T428/31511—Of epoxy ether
    • 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
    • Y10T428/31931—Polyene monomer-containing
    • 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
    • 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
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the present invention relates to new repair films. Moreover, the present invention relates to the use of the new repair films for the repair of the surface of coated substrates.
  • the coating material may also contain water, but in the examples of the three aforementioned patent applications and the above-mentioned American patent, only one coating material is used which contains organic solvent and a radical-polymerizable, acid group-free urethane acrylate having an olefinically unsaturated double bond content of 1.927 eq / kg.
  • the conventional coating materials have the disadvantage that significant amounts of volatile organic solvents are emitted during the production of the coated films. This leads to safety-related and ecological problems with the manufacturer of the coated films. The residues of volatile organic solvents which may still be present in the coated films can also lead to comparable problems for the user, for example in the repair of damaged automotive coatings in the paint shop.
  • coated films for repair purposes whose coatings can be prepared from aqueous coating materials.
  • the object of the present invention is to provide new repair films which comprise a carrier film and at least one layer of a cured or partially cured coating material and which can be produced with the aid of an aqueous coating material.
  • the new repair films are said to be useful in repairing the surface of coated substrates by applying the coated side support film to the site to be repaired, curing the layer of the coating with actinic radiation, and removing the substrate film is hardened through the carrier film or after removal of the carrier film with actinic radiation.
  • the resulting refinishes are intended to meet all the requirements for automotive coatings (see European Patent EP 0 352 298 B1, page 15, lines 42, to page 17, line 40) and their appearance (appearance) of a Class A Surface in full compliance. In particular, they should be weather-resistant, chemical-resistant and scratch-resistant.
  • the new repair films are referred to below as "films according to the invention".
  • the new method for repairing the surface of coated substrates was found, in which one
  • the new method for repairing the surface of coated substrates is referred to as "inventive method”.
  • the first essential component of the film according to the invention is the temporary carrier film (A).
  • Temporal means that the carrier film (A) after its use according to the invention is removed from the inventive refinish coatings prepared by the process according to the invention.
  • Suitable temporary carrier films (A) are all films of plastic films, metal foils and metallized plastic films which have sufficient stability to mechanical stress, thermal energy, actinic radiation and the constituents used in the coating materials (B) to be used according to the invention.
  • plastic films preferably transparent plastic films, are used.
  • plastic films are known from German Patent Application DE 103 35 620 A2, paragraphs [0018] and [0019].
  • temporary carrier films (A) plastic films are used which
  • the temporary carrier film (A) has an adhesion to the curable layers (B), which is strong enough to allow a trouble-free production and storage and a trouble-free transport of the films according to the invention.
  • the adhesion to the curable layers (B) and to the coatings (B) produced by the process according to the invention is not so strong that the respective layers or coatings (B) are damaged during the detachment of the temporary carrier film (A).
  • the withdrawal of the temporary carrier film (A) requires that of the outer surface of the dried, not or only partially cured Layer (s) (B) or the coating (s) (B) which can be produced therefrom have an average force of 10 to 250 mN / cm, in particular 10 to 100 mN / cm.
  • the temporary carrier film (A) is particularly preferably selected from the group consisting of films made from polyethylene, polypropylene, ethylene copolymers, propylene copolymers and ethylene-propylene copolymers.
  • the dried, not or only partially cured layer (s) (B) or the coating (s) (B) which can be produced therefrom particularly preferably has adhesive properties and / or embossing.
  • the embossing may be a pictorial embossing which serves decorative purposes and / or signaling purposes such as lettering.
  • the embossing is an embossment in the micron range, which has a light-scattering effect, so that a matting effect results.
  • the side of the temporary carrier film (A) facing away from the dried, not or only partially cured layer (s) (B) or the coating or layers (B) which can be produced therefrom (B) has antiblocking properties.
  • the temporary carrier film (A) is composed of several layers.
  • At least one, preferably one, homo- or copolymer which is preferably selected from the group consisting of polyethylene, polypropylene, ethylene copolymers, propylene copolymers and ethylene-propylene copolymers, and
  • the thickness of the temporary carrier film (A) can vary widely and depends on the requirements of the individual case. It preferably has a thickness of 10 to 100 ⁇ m, in particular 30 to 70 ⁇ m.
  • the temporary carrier films (A) described above are conventional and known and can be obtained, for example, from Bischoff + Klein, Lengerich, Federal Republic of Germany.
  • the second essential constituent of the film according to the invention is at least one, in particular one, layer (B).
  • the layer (B) covers one side of the temporary carrier film (A) partially, for example imagewise, or completely or substantially completely.
  • the temporary carrier foil (A) is substantially completely covered.
  • Substantially complete means that a small edge area, for example at least one narrow edge strip or at least one corner, of the temporary carrier film (A) remains uncovered, so that the withdrawal of the temporary carrier film (A) is facilitated in the context of the method according to the invention.
  • the layer (B) is dried, d. h. that it is completely or substantially free of water and organic solvents.
  • Substantially free means that the relevant layer (B) has a water content and / or a solvent content of ⁇ 10% by weight, preferably ⁇ 5% by weight and in particular ⁇ 2% by weight, based in each case on the layer (B) has.
  • “Completely free of” means that the water content and / or the solvent content are below the usual and known detection limits for water and organic solvents.
  • the layer (B) is not or only partially cured.
  • Partially cured means that the three-dimensional network that forms during curing or crosslinking does not affect the property profile of the layer (B), but that the layer (B) is still mechanically deformable and in particular thermoplastic and not thermosetting Behavior shows.
  • the layer (B) is curable with actinic radiation.
  • actinic radiation is electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation, X-radiation or gamma radiation, preferably UV radiation, in particular UV-A radiation, and corpuscular radiation, such as electron radiation, proton radiation, Alpha radiation, beta radiation or neutron radiation, in particular electron radiation understood.
  • NIR near infrared
  • UV radiation visible light
  • UV radiation X-radiation or gamma radiation
  • corpuscular radiation such as electron radiation, proton radiation, Alpha radiation, beta radiation or neutron radiation, in particular electron radiation understood.
  • the thickness of the layer (B) can vary very widely and depends on the requirements of the individual case.
  • the layer (B) is preferably 1 to 200 ⁇ m, preferably 5 to 200 ⁇ m, particularly preferably 10 to 100 ⁇ m and in particular 20 to 80 ⁇ m thick.
  • the layer thickness is adjusted so that after curing of the layer (B) with actinic radiation, a coating (B) of a thickness of 5 to 100 .mu.m, preferably 10 to 80 .mu.m and in particular 10 to 70 microns results.
  • the layer thickness of the layer (B) preferably decreases towards the edges of the films according to the invention, ie the layer (B) runs out towards the edges. This results in a coating (B) whose layer thickness varies in the same way. As a result, a conspicuous demolition edge is avoided in the case of the refinish coating according to the invention produced with the aid of the relevant film according to the invention.
  • the layer (B) can be produced from an aqueous coating material (B).
  • the aqueous coating material (B) contains at least one, in particular a free-radically crosslinkable binder (B1)
  • 0.08 to 10 eq / kg preferably 0.1 to 8 eq / kg, more preferably 0.15 to 5 eq / kg, very particularly preferably 0.18 to 3 eq / kg and in particular 0.2 to 2 eq / kg of the binder (B1).
  • the content of acid groups is preferably determined by the acid number according to DIN EN ISO 3682.
  • the olefinically unsaturated double bonds are preferably selected from the group consisting of (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, preferably (meth) acrylate groups.
  • the olefinically unsaturated double bonds are present in acrylate groups.
  • the binders (B1) are oligomeric or polymeric.
  • Oletymer means that the relevant binder (B1) is composed of 3 to 12 monomeric structural units.
  • Polymer means that the relevant binder (B1) is composed of more than 8 monomeric structural units.
  • binder (B1) composed of 8 to 12 monomeric units is considered to be an oligomer or a polymer depends primarily on its number average molecular weight.
  • the number-average molecular weight of the binder (B1) can vary very widely and depends on the requirements of the individual case, in particular the viscosity, which is advantageous for the processing of the binder (B1) and the coating material (B) prepared therewith.
  • the viscosity of the coating material (B) is usually adjusted so that a problem-free application to the temporary carrier film (A) and a slight filming of the resulting layer (B) is achieved during drying.
  • the number-average molecular weight is preferably from 1000 to 50,000 daltons, preferably from 1,500 to 40,000 daltons and in particular from 2,000 to 20,000.
  • the nonuniformity of the molecular weight may likewise vary widely and is preferably from 1 to 10, in particular from 1.5 to 8.
  • Suitable binders (B1) are all oligomers and polymers which have the property profile described above.
  • the binder (B1) is selected from the group consisting of oligomeric and polymeric epoxy (meth) acrylates, urethane (meth) acrylates and carbonate (meth) acrylates.
  • the binder (B1) is selected from the group consisting of oligomeric and polymeric epoxy (meth) acrylates, urethane (meth) acrylates and carbonate (meth) acrylates.
  • the urethane (meth) acrylates can be prepared by reaction of
  • (b1) at least one compound containing at least two isocyanate groups, selected from the group consisting of aliphatic, aromatic or cycloaliphatic di- and polyisocyanates, with
  • (b2) at least one compound having at least one, in particular one, isocyanate-reactive functional group, preferably selected from the group consisting of hydroxyl groups, thiol groups and primary and secondary amino groups, in particular hydroxyl groups, and at least one, in particular one, of the groups described above which contain a free-radically polymerizable olefinically unsaturated double bond, preferably a (meth) acrylate group, in particular an acrylate group .
  • (b3) at least one compound having at least one, in particular one, isocyanate-reactive functional group and at least one, in particular one, acid group, preferably selected from
  • suitable compounds (b1) are customary and known diisocyanates and polyisocyanates having an isocyanate functionality of on average 2 to 6, preferably 2 to 5 and in particular 2 to 4.
  • Aliphatic means that the isocyanate group in question is linked to an aliphatic carbon atom.
  • Cycloaliphatic means that the isocyanate group in question is linked to a cycloaliphatic carbon atom.
  • Aromatic means that the isocyanate group in question is linked to an aromatic carbon atom.
  • Suitable aliphatic diisocyanates (b1) are aliphatic diisocyanates, such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate,
  • Tetradecamethylene diisocyanate derivatives of lysine diisocyanate, Tetramethylxylylidenediisocyanat, trimethylhexane diisocyanate or 1, 3- or 1, 4-bis (isocyanatomethyl) cyclohexane.
  • Suitable cycloaliphatic diisocyanates (b1) are 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, tetramethylcyclohexane diisocyanate, bis (4'-isocyanatocyclohexyl) methane, (4'-isocyanatocyclohexyl) - (2'-isocyanatocyclohexyl) methane, 2,2-bis (isocyanatocyclohexyl) propane, 2,2- (4'-isocyanatocyclohexyl) - (2'-isocyanatocyclohexyl) propane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate) , 2,4- or 2,6-diisocyanato-i-methylcyclohexane or diisocyanates derived from dimer fatty acids, as sold under the
  • aromatic diisocyanates (b1) are 2,4- or 2,6-tolylene diisocyanate or their isomer mixtures, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane or their isomer mixtures, 1,3- or 1, 4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, diphenyl-4,4'-diisocyanate, 4 I 4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane -4,4'-diisocyanate, 1, 4-diisocyanatobenzene or 4,4'-diisocyanato-diphenyl ether.
  • aliphatic and cycloaliphatic diisocyanates (b1) in particular hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and / or di (isocyanatocyclohexyl) methane are used.
  • suitable polyisocyanates (b1) are triisocyanates such as nonane triisocyanate (NTI) and polyisocyanates (b1) based on the diisocyanates and triisocyanates (b1) described above, in particular oligomers containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane , Carbodiimide, urea, uretonimine and / or uretdione groups.
  • suitable polyisocyanates (b1) of this type and processes for their preparation are described, for example, in patents and patent applications CA 2,163,591 A1, US Pat. No. 4,419,513 A, US Pat. No.
  • the oligomers (b1) of hexamethylene diisocyanate and isophorone diisocyanate are used.
  • Examples of suitable compounds (b2) are the monoesters of
  • (b21) diols and polyols which preferably contain from 2 to 20 carbon atoms and at least 2 hydroxyl groups in the molecule, such as
  • Ethylene glycol diethylene glycol, triethylene glycol, 1,2-propylene glycol,
  • Tripropylene glycol tetraethylene glycol, pentaethylene glycol, 1, 4-
  • Trimethylolpropane pentaerythritol, dipentaerythritol, ditrimethylolpropane
  • (b22) alpha, beta-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid,
  • suitable compounds (b2) are the monovinyl ethers of the above-described diols and polyols (b21).
  • suitable compounds (b2) are the monoesters or monoamides of the above-described alpha, beta-unsaturated carboxylic acids (b22) with (b23) amino alcohols, such as 2-aminoethanol, 2- (methylamino) ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-amino)
  • polyamines such as ethylenediamine or diethylenetriamine.
  • hydroxycarboxylic acids such as hydroxyacetic acid (glycolic acid), 2- or 3-hydroxypropionic acid, 3- or 4-hydroxybutyric acid, hydroxypivalic acid, 6-hydroxycaproic acid, citric acid,
  • amino acids such as 6-aminocaproic acid, aminoacetic acid (glycine), 2-aminopropionic acid (alanine), 3-aminopropionic acid (beta-alanine) or the other essential amino acids; N, N-bis (2-hydroxyethyl) glycine, N- [bis (hydroxymethyl) methyl] glycine or imidodiacetic acid,
  • sugar acids such as gluconic acid, glucaric acid, glucuronic acid, galacturonic acid or mucic acid (galactaric acid),
  • sulfonic acids such as 2-aminoethanesulfonic acid (taurine),
  • hydroxyacetic acid (glycolic acid) is used.
  • the acid groups can be ionized.
  • Suitable counterions are lithium, sodium, potassium, rubidium, cesium, magnesium, strontium, barium or ammonium ions and primary, secondary, tertiary or quaternary ammonium ions, which are derived from customary and known organic amines.
  • Suitable compounds (b4) are the above-described compounds diols and polyols (b21), amino alcohols (b23), thio alcohols (b24) or polyamines (b25).
  • the compounds (b1), (b2) and (b3) and optionally (b4) are reacted with each other in a molar ratio such that 3 eq of isocyanate groups from the compound (b1)
  • the preparation of the urethane (meth) acrylates (B1) has no special features, but takes place under the customary and known methods Conditions of the reaction of polyisocyanates with the exclusion of water at temperatures of 5 to 100 0 C.
  • an oxygen-containing gas in particular under air or air-nitrogen mixtures.
  • the content of the aqueous coating material (B) on the binder (B1) can vary very widely.
  • the content is preferably from 20 to 100% by weight, preferably from 30 to 99% by weight, particularly preferably from 40 to 98% by weight, very particularly preferably from 50 to 97% by weight and in particular from 60 to 95% by weight. %, in each case based on the film-forming solid of the aqueous coating material (B1).
  • the film-forming solid of the aqueous coating material may consist of the binder (B1).
  • the coating material (B) also contains at least one customary and known additive (B2), as is customarily used in clearcoats, in customary and known amounts.
  • the additive (B2) from the group consisting of residue-free or substantially residue-free thermally decomposable salts; binders which are physically, thermally and / or actinically radiation-curable with respect to the binders (B); Neutralizing agents; thermally curable reactive diluents; curable with actinic radiation reactive diluents; molecularly soluble dyes; transparent pigments; nanoparticles; Light stabilizers; antioxidants; Venting means; Wetting agents; emulsifiers; slip additives; polymerization inhibitors; Initiators of radical polymerization, especially photoinitiators; thermolabile radical initiators; Adhesion promoters; Leveling agents; film-forming aids; Rheology auxiliaries, such as thickeners and pseudoplastic Sag control agents, SCA; Flame retardants; Corrosion inhibitors; anti-caking agents; To grow; driers; Biocides and matting agents; selected.
  • Neutralizing agents thermally curable reactive dil
  • the aqueous coating material (B) contains residue-free or substantially residue-free thermally decomposable salts, light stabilizers, Wetting agents, emulsifiers, leveling agents, photoinitiators and rheological aids as additives (B2).
  • the aqueous coating material (B) may be a molecular disperse solution or a dispersion.
  • the dispersion in turn may be a suspension or an emulsion.
  • the aqueous coating material (B) is preferably a structurally viscous dispersion which is free or essentially free of volatile organic compounds and which has solid particles as a disperse phase and / or highly viscous particles dimensionally stable under storage and application conditions with a mean particle size z-mean measured by photon correlation spectroscopy from 80 to 750 nm, preferably 80 to 600 nm and in particular 80 to 400 nm.
  • Photon correlation spectroscopy is a common and known method for measuring dispersed particles with particle sizes ⁇ 1 ⁇ m.
  • the measurement can be performed using the Malvern® Zetasizer 1000.
  • the particle size distribution can be adjusted in any way.
  • the particle size distribution results from the use of suitable wetting agents (B2).
  • the viscosity behavior referred to as "structurally viscous” describes a state which, on the one hand, meets the requirements of the application and, on the other hand, also the requirements with regard to storage and settling stability:
  • the pseudoplastic aqueous dispersion (B) In the agitated state, for example when pumping the pseudoplastic aqueous dispersion (B) in the ring line of a coating plant and when applied, the pseudoplastic aqueous dispersion (B) assumes a low-viscosity state which ensures good processability, but without shear stress, the viscosity increases and in this way ensures that the coating material already on the temporary carrier film (A) to be coated (B) shows a reduced tendency to sag on vertical surfaces ("runner").
  • the higher viscosity in the still state such as in storage, leads to settling of the solid Particles is largely prevented or re-stirring during storage time only weakly deposited pseudoplastic aqueous dispersion (B) is guaranteed.
  • the pseudoplastic behavior is preferably adjusted by means of suitable thickeners (B2), in particular nonionic and ionic thickeners (B2), which are present in the aqueous phase.
  • Dispossionally stable means that under the usual and known conditions of storage and application of pseudoplastic aqueous dispersions, the particles only slightly agglomerate, if at all, and / or disintegrate into smaller particles, but also under the influence of shear forces substantially their original shape preserve.
  • the clearcoat slurry (B) to be used according to the invention is preferably prepared by the secondary dispersion process known from German Patent Application DE 199 08 018 A1, German Patent DE 198 41 842 C2 or German Patent Application DE 100 55 464 A1.
  • the ionically stabilizable binders (B1) and optionally the additives (B2) are dissolved in organic solvents, in particular readily volatile, water-miscible solvents.
  • the resulting solutions are dispersed in water with the aid of neutralizing agents (B2).
  • it is diluted with water while stirring. It initially forms a water-in-oil emulsion, which turns on further dilution in an oil-in-water emulsion. This point is generally achieved at solids contents of ⁇ 50 wt .-%, based on the emulsion, and is externally recognizable by a greater drop in viscosity during dilution.
  • the oil-in-water emulsion can also be prepared directly by the melt emulsification of the binder (B1) and optionally the additives (B2) in water.
  • wetting agents (B2) are added to the organic solution and / or the water before or during the emulsification. Preferably, they are added to the organic solution.
  • the solvent-containing emulsion thus obtained is subsequently freed of solvents by azeotropic distillation.
  • the removal-solvent at a distillation temperature below 70 0 C, preferably below 50 0 C and are distilled in particular below 4O 0 C.
  • the distillation pressure is chosen so that this temperature range is maintained at higher boiling solvents.
  • the azeotropic distillation can be accomplished by stirring the emulsion at room temperature in an open vessel for several days.
  • the solvent-containing emulsion is freed from the solvents by vacuum distillation.
  • the evaporated or distilled off amount of water and solvents are replaced by water to avoid high viscosities.
  • the addition of the water can be done before, after or during the evaporation or distillation by adding in portions.
  • the glass transition temperature of the dispersed dimensionally stable particles increases, and instead of the previous solvent-containing emulsion, the pseudoplastic aqueous dispersion (B) is formed, i. the clearcoat slurry (B), off.
  • the dimensionally stable particles are mechanically comminuted in the wet state, which is also referred to as wet milling.
  • wet milling Preferably conditions 60 and in particular 5O 0 C in this case be applied so that the temperature of the ground material 70 preferably does not exceed.
  • the specific energy input during the milling process is preferably 10 to 1000, preferably 15 to 750 and in particular 20 to 500 Wh / g.
  • suitable devices which produce low shear fields are customary and known stirred tanks, gap homogenizers, microfluidizers or dissolvers.
  • Examples of suitable devices which produce high shear fields are conventional and known stirred mills or inline dissolvers.
  • the devices that produce high shear fields are used.
  • the agitator mills according to the invention are particularly advantageous and are therefore used with very particular preference.
  • the slurry according to the invention is fed to the devices described above with the aid of suitable devices, such as pumps, in particular gear pumps, and driven over it in a circle until the desired particle size is reached.
  • suitable devices such as pumps, in particular gear pumps
  • the clearcoat slurry (B) advantageously has a solids content of 10 to 60 wt .-%, in particular from 20 to 50 wt .-%, on.
  • the clearcoat slurry (B) is filtered before use.
  • the usual and known filtration devices and filters are used.
  • the mesh size of the filters can vary widely and depends primarily on the particle size and the particle size distribution of the particles. The person skilled in the art can therefore easily determine the suitable filters on the basis of this physical parameter. Examples of suitable filters are monofilament surface filters or bag filters. These are available on the market under the brands Pong® or Cuno®.
  • the film according to the invention can be produced by coating one side of the temporary carrier film (A) with at least one, in particular one, aqueous coating material (B), in particular a clearcoat slurry (B). Subsequently, the resulting layer (s) will become or
  • Layers (B) are not or only partially cured. In particular, working under exclusion of actinic radiation.
  • the application of the aqueous coating material (B), in particular the clearcoat slurry (B), offers no special features, but can be carried out by means of the customary and known methods of applying liquid coating materials, such as e.g. Spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling, take place.
  • the application can be carried out continuously, for example in a film coating plant, or discontinuously, for example with already cut temporary carrier films (A).
  • the aqueous coating material (B), in particular the clearcoat slurry (B), is preferably applied in such a way that the layer (B) runs out towards the edges of the film according to the invention.
  • the aqueous coating material (B), in particular the clearcoat slurry (B), dries without problems and shows film formation at the processing temperature, generally at room temperature. That is, the applied as a wet layer clearcoat slurry (B) releases at room temperature or slightly elevated temperatures with release of water, wherein the particles contained therein change their original shape and flow together.
  • the drying may be accelerated by the use of a gaseous, liquid and / or solid hot medium such as hot air, heated oil or heated rolls, or microwave, infrared and / or near infrared (NIR) light. It is important to ensure that no complete crosslinking occurs by thermally initiated radical polymerization.
  • the wet layer is in a convection oven at 23 to 150 0 C, preferably 30 to 120 0 C and in particular 50 to 100 ° C dried.
  • the resulting film (A / B) according to the invention can be used in accordance with the invention.
  • the outer surface of the layer (B) or of the layers (B) can also be partially, for example imagewise, or completely, coated with at least one further, not or only partially cured, physically, thermally and / or actinic radiation-curable layer (C) be coated.
  • the layer (s) (C) is or are selected from the group consisting of layers which serve to prepare color and / or effect basecoats, surfacer coats and antistonechip primers.
  • coating materials can be used.
  • basecoats in particular aqueous basecoats, aqueous, conventional or pulverulent fillers and aqueous, conventional or pulverulent coating materials for the production of
  • Rockfall protection primers used They are applied using the customary and known application methods and devices and then dried.
  • the films according to the invention can be excellently adapted to the structure and the material composition of the coatings to be repaired.
  • the films (A / B) or (A / B / C) according to the invention are outstandingly suitable for the repair of damaged areas on or in the surface of coated substrates. Because of their advantageous mechanical properties, the films according to the invention also excellently adapt to the surface of complex-shaped substrates.
  • the substrates of metals, plastics, wood, ceramics, stone, textile, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, and composites of these materials.
  • the substrates can be coated in many different ways.
  • films according to the invention are used whose layers (B) or (B) and (C) have the same or substantially the same structure and / or the same or substantially the same material composition as the corresponding layers in the coatings to be repaired.
  • the films of the invention are excellent for the repair of the coatings
  • Containers such as coils, containers or packaging, - electrotechnical components, optical components, mechanical components and white goods, such as domestic appliances, boilers and radiators,
  • the repair small area for example, as a spot repair, or large area both the car manufacturer in the line, for example, as an end-of-line repair, as well as in the paint shop done.
  • the films of the invention can be easily tailored to the appropriate size.
  • the damaged surfaces can be pretreated in the area of the areas to be repaired. This can be done for example by dissolving the surface with an organic solvent, heads, grinding, corona treatment or flame treatment. It is a particular advantage of the process according to the invention and of the films according to the invention that in many cases such pretreatments can be dispensed with.
  • At least one film according to the invention is laminated with its coated side onto the point (s) to be repaired.
  • pressure and / or heat can be applied.
  • the layer (B) of the laminated film according to the invention is cured with actinic radiation.
  • the irradiation can take place through the temporary carrier film (A). This can also be deducted before the irradiation. However, the irradiation can also be carried out before and after removal of the temporary carrier film (A).
  • the irradiation preferably takes place through the temporary carrier foil (A), because this excludes the inhibiting influence of the atmospheric oxygen and the complete hardening occurs particularly rapidly.
  • the curing with actinic radiation can still be supported by heat, the methods described above and
  • the heat energy can come from the radiation sources of actinic radiation.
  • the Heat treatment may be carried out before, during and / or after irradiation with actinic radiation. Likewise, it can be carried out before and / or after the removal of the temporary carrier film (A).
  • the laminated films according to the invention also comprise layers (C) which are curable with actinic radiation, they are completely cured together with the layers (B).
  • a heat treatment can also take place here.
  • a heat treatment is particularly recommended when the layers (C) are physically and / or thermally curable.
  • the heat treatment is advantageously carried out at temperatures at which the substrates are not thermally damaged.
  • the curing with actinic radiation preferably UV radiation, in particular UV-A radiation
  • actinic radiation preferably UV radiation, in particular UV-A radiation
  • the damaged areas repaired in accordance with the method according to the invention fit visually excellently into the surface of the coated substrates and are no longer visually recognizable. Because they no longer have any demolition edges or only negligible demolition edges, the repaired damaged areas can no longer be felt. They meet all the requirements placed on automotive finishes (see European Patent EP 0 352 298 B1, page 15, lines 42, to page 17, line 40) and correspond in their appearance to a Class A surface in in full. In particular, they are weather-resistant, chemical-resistant and scratch-resistant.
  • Isopropenylidenedicyclohexanol was coarsely dispersed in hydroxyethyl acrylate at 6O 0 C with stirring.
  • the polyisocyanates pentaerythritol tri / tetra-acrylate, hydroquinone monomethyl ether, 1,6-di-tert-butyl-p-cresol and methyl ethyl ketone.
  • dibutyltin dilaurate the reaction mixture warmed. The mixture was stirred at 75 ° C for several hours until the content of free isocyanate groups was constant. Then glycolic acid and methanol were added and stirred until no more free isocyanate groups were detectable.
  • Pentaerythritol tri / tetra-acrylate (average OH number: 100 to 111 mg KOH / g) 24.7 eq OH
  • the resulting binder (B1) had a glass transition temperature of 2.5 ° C, a viscosity at 23 ° C of 2.0 Pas, a content of olefinically unsaturated double bonds of 3.12 eq / kg solids and an acid number of 11, 41 mg KOH / g solids on. It was outstandingly suitable for the production of aqueous coating materials (B).
  • the resulting mixture was dispersed in 1,005 parts by weight of deionized water. To this dispersion were added 0.117 parts by weight of ammonium acetate added. The degree of neutralization of the binder (B1) was 75%. Subsequently, dispersion was filtered through a filter 1 ⁇ m Cuno® white.
  • the filtered dispersion was stirred for 24 hours at room temperature in an open vessel to evaporate the methyl ethyl ketone.
  • the solvent-free dispersion was completed with 0.788 parts by weight of Baysilone® AI 3468 (leveling agent from Borchers) and 15.78 parts by weight of Acrysol® RM-8W (nonionic associative thickener from Rohm & Haas).
  • the mean particle size z-mean of the resulting clearcoat slurry was measured by means of photon correlation spectroscopy (Malvern Zetasizer® 1000); it was 140 nm.
  • the clearcoat slurry had a solids content of 36.2% by weight. It was excellently suited for the production of repair foils.
  • the film GH-X527 from Bischof + Klein, Lengerich, Federal Republic of Germany was used as a temporary carrier film (A).
  • the essential properties of this film are described in the German patent application DE 103 35 620 A1, Table 1, page 10.
  • the film had an outside with anti-blocking properties.
  • Your page to be coated had adhesive properties.
  • the temporary carrier film (A) was coated with the clearcoat slurry of Preparation Example 2.
  • the resulting wet layer (B) was dried at 30 ° C. in a circulating air oven.
  • the resulting dried, uncured layer (B) was 50 ⁇ m thick.
  • sample sheets were used, which had been coated with an automotive OEM finish corresponding multi-layer coating of electrocoating, surfacer, black basecoat and clearcoat.
  • the clearcoats of the multicoat paint systems were each ground at one point with abrasive paper (particle sizes 600 ⁇ m to 1200 ⁇ m).
  • the damaged areas were covered with the repair film according to Example 1.
  • the clearcoat films (B) came to lie on the clearcoats of the sample sheets.
  • the laminated repair films were heated to 60 to 80 0 C with an infrared radiator.
  • the laminated repair films were exposed to UV radiation through the temporary carrier sheets (A) (1.5 J / cm 2 , ILD light bug 390, IST unit), whereby the clearcoat films (B) were completely cured. Subsequently, the temporary backing sheets (A) were peeled off.
  • the resulting refinishes had an excellent visual impression.
  • the adhesion on the old paintwork was excellent (crosshatch test with tape tear: grade GT 0-1). They had a smooth surface and excellent gloss. In addition, they were resistant to chemicals, hard and scratch-resistant, which could be substantiated by the results below.
  • Tree resin > 75 ° C

Landscapes

  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne des films pour réparation que l'on produit (1) en revêtant une face d'un film support temporaire (A) d'au moins une substance de revêtement aqueuse (B) qui contient au moins un agent liant réticulable radicalairement (B1) ayant une température de transition vitreuse comprise entre -70 et +50 °C, une teneur en liaisons doubles oléfiniquement insaturées comprise entre 2 et 10 eq/kg ainsi qu'une teneur en groupes d'acide comprise entre 0,05 et 15 eq/kg et (2) en séchant la ou les couches résultantes (B) mais sans les durcir ou en ne les durcissant que partiellement. L'invention concerne également un procédé pour réparer la surface de substrats enduits, selon lequel (I) on lamine la face enduite d'au moins un des films pour réparation selon l'invention sur le ou les endroits à réparer de la surface du substrat et (II) on durcit complètement par rayonnement actinique la ou les couches durcissables (B) avant ou après avoir enlevé le film support temporaire (A).
EP06840929A 2005-11-10 2006-11-09 Films pour reparation et leur utilisation Withdrawn EP1945377A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510053661 DE102005053661A1 (de) 2005-11-10 2005-11-10 Reparaturfolien und ihre Verwendung
PCT/EP2006/010717 WO2007054288A1 (fr) 2005-11-10 2006-11-09 Films pour reparation et leur utilisation

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US9573164B2 (en) 2013-03-15 2017-02-21 Akzo Nobel Coatings International B.V. Dry primer film composite and use thereof
CN104130727B (zh) * 2014-08-06 2016-06-01 华进半导体封装先导技术研发中心有限公司 一种压敏临时键合胶的制备方法及其应用
US9908692B2 (en) 2015-05-06 2018-03-06 ASFI Partners, L.P. Multi-piece storage tank pad with separate connectors

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DE102005053661A1 (de) 2007-05-16
WO2007054288A1 (fr) 2007-05-18
US8337649B2 (en) 2012-12-25

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