EP0382749A1 - Enduit a base d'un copolymere d'acrylate avec des groupes de production et son utilisation - Google Patents

Enduit a base d'un copolymere d'acrylate avec des groupes de production et son utilisation

Info

Publication number
EP0382749A1
EP0382749A1 EP88908194A EP88908194A EP0382749A1 EP 0382749 A1 EP0382749 A1 EP 0382749A1 EP 88908194 A EP88908194 A EP 88908194A EP 88908194 A EP88908194 A EP 88908194A EP 0382749 A1 EP0382749 A1 EP 0382749A1
Authority
EP
European Patent Office
Prior art keywords
weight
hydroxyl
coating
koh
acrylate
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.)
Pending
Application number
EP88908194A
Other languages
German (de)
English (en)
Inventor
Werner Alfons Jung
Udo Vorbeck
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 Farben und Fasern AG
Original Assignee
BASF Lacke und Farben AG
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 Lacke und Farben AG filed Critical BASF Lacke und Farben AG
Publication of EP0382749A1 publication Critical patent/EP0382749A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof

Definitions

  • Coating agent based on an acrylate copolymer with hydroxyl, carboxyl and tertiary amino groups, process for producing the coating agent and its use
  • the invention relates to coating compositions consisting of
  • Coating agents based on acrylate copolymers containing hydroxyl groups, which can be cured with polyisocyanates and contain groups which accelerate the formation of urethane, are known.
  • EP-A-52 233 describes a process for the preparation of acrylate copolymers by copolymerization of acrylic or methacrylic acid esters, hydroxyalkyl esters of acrylic or methacrylic acid, acrylic or methacrylic acid and, if appropriate, neutral monomers and Combination of these carboxyl group-containing polyacrylates with suitable crosslinking agents.
  • melamine-formaldehyde condensates are used as crosslinking agents.
  • EP-B-39 797 discloses copolymers of (meth) acrylic acid esters, monomers with at least one hydroxyl group, monomers with at least one tertiary amino group and optionally other copolymerizable monomers.
  • the acrylate copolymers crosslinkable with polyisocyanates are used in pressure sensitive adhesives.
  • the compositions described have an almost unlimited pot life.
  • a coating composition which contains a hydroxyl-containing acrylate copolymer which contains in a proportion of 10 to 40% by weight of monomers having tertiary amino groups, preferably N-vinylpyrrolidone, in copolymerized form.
  • the copolymer can contain up to about 5% by weight of built-in monomers containing carboxyl groups.
  • the coating agents described are used to coat chrome-plated surfaces and protect against demolition and moisture.
  • the copolymers crosslinked with polyisocyanates lead to coatings with good adhesion to chromium, chromium alloys, aluminum and aluminum alloys.
  • the relatively high proportion of amine monomers is necessary for good adhesion to the metal surfaces mentioned.
  • DE-OS 29 00 592 describes hydroxyl-containing acrylate copolymers with tertiary amino groups and optionally carboxyl groups. These polyacrylates are produced in a two-stage process. First, in a first stage 3 to 30% by weight of the glycidyl ester of acrylic or methacrylic acid, 0 to 20% by weight of a hydroxyalkyl ester of acrylic or methacrylic acid, 5 to 60% by weight of neutral monomers, 5 to 70% by weight. % of an acrylic acid ester or methacrylic acid ester and 0 to 10% by weight of an ⁇ , ⁇ -monoolefinically unsaturated mono- or dicarboxylic acid with free-radical polymer siert.
  • the glycidyl groups of the copolymer are then reacted with a secondary amine containing secondary hydroxyl groups while largely maintaining the hydroxyl function.
  • a secondary amine containing secondary hydroxyl groups When using monomers containing carboxyl groups there is a risk of premature gelation of the prepolymer by reaction of the carboxyl groups with the epoxide groups of the glycidyl ester of acrylic or methacrylic acid. If hydroxyalkyl esters of acrylic or methacrylic acid are used which contain a primary hydroxyl group, there is also the risk of an undesirable side reaction with the glycidyl groups present.
  • binders for cathodic electrocoating in which a hydroxyl-containing polymer (P) with (PA) compounds which have at least one tertiary amino group and an average of 0.8 to 1.5 free Contain isocyanate groups per molecule, and optionally with (PO) compounds containing 0.8 to 1.5 free isocyanate groups and 1 to 3 olefinic double bonds per molecule.
  • P hydroxyl-containing polymer
  • PA tertiary amino group
  • PO PO
  • the acid number acrylic resins are extremely low, since carboxyl groups interfere with the cathodic deposition of the coating agents.
  • the hardening of the binders takes place thermally in DE-OS 28 36 830, optionally supported by adding the above
  • JP-A 79 61 234 describes polyisocyanates curable binders containing hydroxyl groups, which are obtained by reacting vinyl components containing hydroxyl groups with unsaturated carboxylic acids, vinyl components containing basic nitrogen atoms, other comonomers and a catalyst.
  • these binders cannot be used for clear and top coats.
  • Another disadvantage with regard to the solvent load in the environment when drying the paint films is the high viscosity of the binder solutions, e.g. of 30 dPas with a solids content of only 45% in the example given in the abstract 142199 z of the Chemical Abstracts, Volume 91, No. 18, October 29, 1979, page 70.
  • the object of the present invention was to provide coating compositions based on hydroxyl-containing acrylates and on the basis of polyisocyanates, which should have a sufficiently long and in particular easily controllable pot life starting from paint mixtures and which should harden quickly at low temperatures even without the addition of catalyst.
  • the use of these coating agents as clear and top coats should in particular lead to non-yellowing films which at the same time have high flexibility, scratch resistance and weather, solvent and acid resistance.
  • the solids content of the coating solution should be as high as possible with a viscosity that is favorable for processing in order to keep the solvent load in the environment as low as possible when drying the coating films.
  • the coating should can be produced from as many different, readily available raw materials as possible in order to achieve the greatest possible range of application of the coating agents.
  • a dispersion resin is known from US Pat. No. 4,339,365, which consists of an acrylate copolymer with carboxyl groups, hydroxyl groups and tertiary amino groups.
  • the acrylate copolymer can be prepared, for example, by copolymerizing 20 to 85% by weight of alkyl methacrylates with 3 to 8 carbon atoms in the alkyl radical and 5 to 60% by weight of curing monomers, such as e.g.
  • the resin is used to disperse pigments and is processed together with a main film-forming binder, pigments and solvents to form a coating composition. This contains about 25% to about 98% by weight of the main binder, about 1 to about 70% by weight of pigments and about 1 to about 50% by weight of the dispersing resin described, which contains the pigments in a carrier liquid and in the main binder dispersed.
  • the object of the present invention is achieved by a coating agent consisting of
  • the hydroxyl-containing acrylate copolymer (F) is reacted with compounds (G) which contain on average 0.8 to 1.5 - preferably 1 - free isocyanate group and at least 1 tertiary amino group per molecule, the amount of these compounds (G) being chosen in this way is that the resulting acrylate resin (A) has an amine number of 1 to 10 mg KOH / g, preferably 1 to 5 mg KOH / g.
  • Hydroxyalkyl esters of ⁇ , ⁇ -unsaturated carboxylic acids with primary or secondary hydroxyl groups are suitable as component Ia). If a high reactivity of the acrylate copolymer is desired, only hydroxyalkyl esters with primary hydroxyl groups can be used; if the polyacrylate is to be less reactive, only hydroxyalkyl esters with secondary hydroxyl groups are used.
  • hydroxyalkyl esters with primary hydroxyl groups Mixtures of hydroxyalkyl esters with primary hydroxyl groups and hydroxyalkyl esters with secondary hydroxyl groups can of course also be used.
  • suitable hydroxyalkyl esters of ⁇ , ⁇ -unsaturated carboxylic acids with primary hydroxyl groups are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates.
  • Examples of usable hydroxyalkyl esters with a secondary hydroxyl group are 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates.
  • component I.a) can be at least partially a reaction product of one mole of hydroxyethyl acrylate and / or hydroxyethyl methacrylate and an average of two moles of ⁇ -caprolactone.
  • a reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary ⁇ -carbon atom is used as component I.a).
  • Glycidyl esters of strongly branched monocarboxylic acids are available under the trade name "Cardura”.
  • the reaction of acrylic acid or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary ⁇ -carbon atom can take place before, during or after the polymerization reaction. Care must be taken that the acid number of the finished polyacrylate is in the range from 5 to 30 mg KOH / g.
  • component Ib for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid and half esters of maleic and fumaric acid and mixtures thereof are used.
  • Suitable further monomers with a polymerizable, olefinically unsaturated double bond are styrene, vinyl toluene, alkyl esters of acrylic and methyl acrylic acid, alkoxyethyl acrylates and aryloxyethyl acrylates and the corresponding methacrylates and esters of maleic and fumaric acid.
  • Examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyl acrylate, isoamylacrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, pylacrylate, 3,5,5-trimethylhexyl acrylate, decyl acrylate, decyl acrylate, decyl acrylate, Hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, butoxyethyl methacrylate, methyl methacrylate,
  • the compounds (G) used to introduce the tertiary amino group into the acrylate copolymer (F) are prepared by reacting diisocyanates or polyisocyanates with a stoichiometric deficit on a tertiary amine. Suitable for this reaction are tertiary amines of the general formula NR 1 R 2 R 3 , where R 1 is an alkanol or hydroxyphenyl radical and R 2 or R 3 can be alkyl or cycloalkyl radicals. Dialkylalkanolamines such as dimethylethanolamine, diethylethanolamine and their higher homologs or isomers are preferred.
  • suitable diisocyanates or polyisocyanates are: aromatic isocyanates such as, for example, 2,4-, 2,6-tolylene diisocyanate and mixtures thereof, 4,4'-diphenylmethane diisocyanate, m-phenylene, p-phenylene, 4,4'-diphenyl -, 1,5-naphthalene, 1,4- Naphthalene, 4,4'-toluidine, xylylene diisocyanate and substituted aromatic systems such as dianisidine diisocyanates, 4,4'-diphenyl ether diisocyanates or chlorodiphenylene diisocyanates and higher functional aromatic isocyanates such as 1,3,5-triisocyanatobenzene, 4,4 '-, 4 " Triisocyanate triphenylmethane, 2,4,6-triisocyanatotoluene and 4,4'-diphenyldimethylmethane-2, 2 ', 5,5'-te
  • Diisocyanates with different reactive isocyanate groups are preferably used, e.g. Isophorone diisocyanate.
  • the reaction between the amine and the isocyanate is carried out at temperatures from 0 to 80 ° C, preferably from 20 to 50 ° C.
  • the proportions of the reactants are chosen so that the compound (G) formed contains 0.8 to 1.5, preferably 1, free isocyanate group.
  • the polyisocyanates (component B)) used for crosslinking the acrylate resins A) are the same polyisocyanates that are also used for the preparation of the compound (G). For suitable examples, reference is therefore made to the description of compound (G). Furthermore, the polyisocyanates can also be linked to prepolymers with a higher molecular weight. Adducts of tolylene diisocyanate and trimethylolpropane, one of 3 molecules, should be mentioned here
  • Hexamethylene diisocyanate formed biuret and the trimers of hexymethylene diisocyanate and 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane.
  • the amount of crosslinking agent used is chosen so that the ratio of the isocyanate groups of component B) to the hydroxyl groups of component A) is in the range from 0.3: 1 to 3.5: 1. Since the amino and carboxyl groups built into the acrylate copolymer catalyze the formation of polyurethane, the use of an external catalyst can often be dispensed with.
  • amines such as e.g. Dimethylethanolamine used.
  • amines such as e.g. Dimethylethanolamine used.
  • suitable catalysts are tin and zinc organic compounds and other heavy metal accelerators. The amount of catalyst added is 0.01 to 1 wt .-%, based on the solids content of the reacting components.
  • the coating compositions of the invention can be cured at low temperatures, up to about 100 ° C. They can contain common additives and additives from polyurethane coating technology, e.g. Leveling agents based on cellulose esters, oligoalkyl acrylates, silicone oils, plasticizers, such as phosphoric acid esters, phthalic acid esters, pigments and fillers, viscosity-controlling additives, matting agents, UV absorbers and light stabilizers.
  • tertiary monoalcohols can be used to extend the pot life.
  • suitable alcohols which extend pot life are t-butanol and 1-methoxy-2-methyl-propan-2-ol.
  • the pot life of the coating compositions according to the invention can be controlled. It is dependent on the amine number, since amino groups catalyze urethane formation, on the level of the hydroxyl number and on the type of crosslinkable hydroxyl groups present.
  • the pot life of the compositions according to the invention is dependent on the acid number, since urethane formation is accelerated by acid groups and, of course, on the amount of tertiary alcohol added to increase pot life.
  • the coating compositions according to the invention can optionally also contain small proportions of other binders crosslinkable with polyisocyanates.
  • the invention also relates to processes for the preparation of the coating compositions according to the invention, in which the acrylate resin A) is produced in that
  • the hydroxyl-containing acrylate copolymer (F) is reacted with compounds (G), which per Molecule contain on average 0.8 to 1.5, preferably 1, free isocyanate group and at least 1 tertiary amino group, the amount of these compounds (G) being chosen so that the resulting acrylate resin A) has an amine number of 1 to 10 mg KOH / g, preferably 1 to 5 mg KOH / g.
  • This acrylate resin A) is processed with a polyisocyanate B) with at least 2 isocyanate groups per molecule, organic solvent, optionally pigments, fillers and customary auxiliaries and additives, and optionally with a catalyst for crosslinking by mixing and, if appropriate, dispersing to give a coating composition with the proviso that the ratio of the isocyanate groups of B) to the hydroxyl groups of A) is in the range from 0.3: 1 to 3.5: 1.
  • the polymerization reaction for the preparation of component (F) is carried out according to the generally customary methods for polymerizations.
  • the solvent used as the polymerization medium can be selected, for example, from the group of toluene, xylene, chlorobenzene, butyl acetate, ethyl acetate, ethyl glycol acetate, pentyl acetate, tetrahydrofuran, dioxane, acetone and methyl ethyl ketone.
  • the copolymerization temperature depends on the selection of the polymerization initiator.
  • Suitable initiators are peroxide compounds such as dibenzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, 2,2-di-tert-butyl peroxybutane, tert-amyl perbenzoate, 1,3-bis (tert.
  • -butylperoxyisopropyl) -benzene diisopropylbenzene monohydroperoxide and diacyl peroxides, such as, for example, diacetyl peroxide, peroxyketals, such as, for example, 2,2-di- (tert-amylperoxy) propane and ethyl-3,3, -di (tert-amylperoxy) butyrate; aliphatic azo compounds, such as, for example, azobisisobutyronitri 1 and azobiscyclohexanenitrile or thermolabile highly substituted ethane derivatives, for example based on benzpinacol and based on silyl-substituted ethane derivatives.
  • the amount of the individual components a), b), c) is chosen so that an acrylate copolymer with an acid number of 5 to 30 mg KOH / g, preferably 8 to 25 mg KOH / g, is formed.
  • tertiary amino groups are introduced into the acrylate copolymer (F) containing hydroxyl and carboxyl groups in a simple manner from a wide range of raw materials by reaction with compounds (G).
  • the acrylate copolymer (F) is dissolved in an isocyanate-containing solvent such as ethylene glycol monoethyl ether acetate, xylene, toluene, chlorobenzene, more highly substituted aromatics such as solvent Naphthta ® , heavy benzene, various Solvesso ® types, various Shellsol ® types and Deasol ® as well as higher-boiling aliphatic and cycloaliphatic hydrocarbons, such as various white spirits, mineral turpentine, tetralin and decalin as well as esters such as butyl acetate, pentyl acetate, hexylacetate and methoxypropylacetate dissolved and with an isocyanate-containing solvent such as ethylene glyco
  • the acrylate copolymers A) have average molecular weights of 1000 to 10,000, and their solutions in esters zen at 23 ° C a viscosity of 0.5 to 10 dPas at a concentration of 50 wt .-%.
  • Component Ia) can advantageously be at least partially a reaction product of one mole of hydroxyethyl acrylate and / or hydroxyethyl methacrylate and an average of 2 moles of ⁇ -caprolactone.
  • Component Ia) advantageously consists at least partially of a reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary ⁇ -carbon atom.
  • tertiary monoalcohols in the process according to the invention, up to 15% by weight, based on the total weight of the coating composition, of one or more tertiary monoalcohols can be added to the coating composition in order to extend the pot life.
  • the invention also relates to a method for producing a coating, in which the coating agent according to the invention described above is applied to the substrate in the form of a film by spraying, flooding, dipping, rolling, knife coating or brushing, and the film at temperatures up to about
  • the coating compositions according to the invention can be applied to a substrate in the form of a film by any desired methods of coating technology.
  • the coating agents according to the invention have favorable pot lives which, as already explained, can be shortened or lengthened slightly depending on the application.
  • the compositions are curable at low temperature and with short curing times.
  • the resulting films are petrol-resistant, flexible, scratch-resistant, weather-resistant, very good solvent and acid-resistant. In particular, they have no tendency to yellowing.
  • the coating agents described cure at low temperatures, they are particularly well suited for use as automotive refinish paints.
  • compositions are furthermore particularly well suited for use as a clear coat or pigmented top coat, since they have no tendency to yellowing.
  • compositions according to the invention are particularly suitable for use in the formulation of clearcoats for metal-pigmented two-coat coatings ("2-coat-1-bake” process).
  • the coating compositions of the invention lead to coatings with improved results in terms of pendulum hardness and solvent resistance. This is evident from comparative experiments with coating compositions based on acrylate resins which contain only hydroxyl groups and carboxyl groups or hydroxyl groups and tertiary amino groups as functional groups. Furthermore, the dried paint films produced with the coating compositions according to the invention have very low color values. Preparation of the acrylic resin solutions I, II and III
  • the mixtures are heated to 140 C, then the following components are evenly metered in from the monomer tank within 3 h:
  • the following components are evenly metered from the initiator tank within 3.5 h:
  • the acrylic resin solutions obtained have the following values:
  • Resin solution I is therefore an OH polyacrylate with amino groups and a very low acid number
  • resin solution II is an OH polyacrylate with carboxyl groups but without amino groups
  • resin solution III is an OH polyacrylate according to the invention with carboxyl and amino groups.
  • the crosslinker solution is a 75% solution of a trifunctional aliphatic polyisocyanate with a biuret structure based on hexamethylene diisocyanate, dissolved in 1-methoxypropylacetate-2 / xylene 1: 1 (trade name of the crosslinker solution: Desmodur N75 from Bayer AG). Testing of the coating agents based on the acrylic resin solutions I, II and III and the polyisocyanate hardener component
  • the acrylate resin solutions I, II, III are mixed with the hardener solution in such a way that the crosslinking ratio of the OH groups to the NCO groups is 1: 1 in each case.
  • a flow time in the DIN 4 cup of approx. 20 s is set.
  • Pendulum hardness (according to König) (s) 24 h after crosslinking at 60 ° C 55 87 130
  • a clear lacquer was applied to the basecoat based on acrylate resin solution III and dried.
  • a commercially available silver-metallic ic basecoat with the binder components cellulose acetobutyrate / polyester / melamine resin was used. This was applied to filled bonder sheet.
  • Master varnish and crosslinker solution are mixed in a volume ratio of 2: 1 and adjusted to 16 s with dilution (DIN-4 flow cup).
  • the clear coat is sprayed onto the basecoat mentioned above and dried at 60 ° C. for 30 minutes.
  • the film thickness of the clearcoat was 90 ⁇ m.
  • a gloss level (60 °) of 97% was measured.
  • the DOI was 95.
  • the clear lacquer panel was artificially weathered in a Weather-o-Meter with edge filter A (VDA test sheet 621-4, test according to point 3.2). The clear lacquer did not crack until after 4000 h.
  • the pot life was determined from the mixture of master varnish / hardener solution. After 5 hours the viscosity had increased from 16s to 29s (Din-4 flow cup).
  • the lacquer mixture was knife-coated on glass plates and the pendulum hardness was determined according to König with a dry film thickness of 20 ⁇ m.
  • the color number of the acrylate resin solution III was determined according to Gardner; a value of 1 was reached.
  • an acrylate resin was built up, in which the same monomers as for the acrylate resin III were used in the first stage for the preparation of the acrylate copolymer except for the hydroxypropyl acrylate, which was replaced by hydroxyethyl methacrylate.
  • 1% of dimethylaminoethyl methacrylate was additionally polymerized in in the first stage instead of reacting the acrylate copolymer with a compound (G) in a second stage.
  • Azobis (2-methylbutanenitrile) was used as the initiator.
  • the Gardner color number of this acrylic resin is 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Des enduits contiennent en tant que constituants de liants essentiels une résine d'acrylate (A) avec des groupes hydroxyles, carboxyles et amino tertiaires et en tant qu'agent de réticulation (B) des polyisocyanates. On prépare la résine d'acrylate (A) en copolymérisant premièrement entre 10 et 40 % en poids, de préférence entre 15 et 35 % en poids, d'acides carboxyliques alpha, beta-insaturés d'hydroxyalkylester, entre 0,1 et 8 % en poids, de préférence entre 0,5 et 4 % en poids, d'acides carboxyliques éthyléniquement insaturés, et entre 60 et 90 % en poids d'autres monomères avec une liaison double oléfiniquement insaturée. On convertit ensuite le copolymère d'acrylate ainsi obtenu avec des composés (G) qui contiennent par molécule de préférence un groupe isocyanate libre et au moins un groupe amino tertiaire. Ces enduits contiennent en outre des solvants organiques, éventuellement des pigments, des charges et des additifs usuels, ainsi que le cas échéant un catalyseur de la réticulation. L'invention concerne un procédé de production de ces enduits et leur utilisation en peinture automobile en tant que laque transparente, en tant que laque pigmentée de revêtement ou en tant que laque transparente appliquée sur une laque de base lors du laquage avec des laques métalliques pigmentées à deux couches selon un procédé fraîche-à-fraîche.
EP88908194A 1987-09-19 1988-09-10 Enduit a base d'un copolymere d'acrylate avec des groupes de production et son utilisation Pending EP0382749A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873731652 DE3731652A1 (de) 1987-09-19 1987-09-19 Ueberzugsmittel auf der basis eines acrylatcopolymerisats mit hydroxyl-, carboxyl- und tertiaeren aminogruppen, verfahren zur herstellung des ueberzugsmittels sowie seine verwendung
DE3731652 1987-09-19

Publications (1)

Publication Number Publication Date
EP0382749A1 true EP0382749A1 (fr) 1990-08-22

Family

ID=6336456

Family Applications (2)

Application Number Title Priority Date Filing Date
EP19880114851 Expired - Lifetime EP0308756B1 (fr) 1987-09-19 1988-09-10 Matière de revêtement à base d'un polymérisat d'acrylate ayant des groupes hydroxy, carboxyle et aminotertiaires, procédé de préparation de la matière de revêtement et son utilisation
EP88908194A Pending EP0382749A1 (fr) 1987-09-19 1988-09-10 Enduit a base d'un copolymere d'acrylate avec des groupes de production et son utilisation

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP19880114851 Expired - Lifetime EP0308756B1 (fr) 1987-09-19 1988-09-10 Matière de revêtement à base d'un polymérisat d'acrylate ayant des groupes hydroxy, carboxyle et aminotertiaires, procédé de préparation de la matière de revêtement et son utilisation

Country Status (6)

Country Link
EP (2) EP0308756B1 (fr)
AT (1) ATE78272T1 (fr)
BR (1) BR8807707A (fr)
DE (2) DE3731652A1 (fr)
ES (1) ES2042669T3 (fr)
WO (1) WO1989002452A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4037961C2 (de) * 1990-11-29 1994-12-08 Erwin Fendrich Verfahren zum plastischen Gestalten von Bildern und Abbildungen
DE4143688B4 (de) 1991-03-30 2007-03-29 Basf Coatings Ag Verwendung eines Mischsystems sowie Verfahren zur Herstellung von Wasserbasislacken und von wasserverdünnbaren Überzugsmitteln
DE4132430A1 (de) * 1991-09-28 1993-04-01 Basf Lacke & Farben Waessrige lacke und verfahren zur herstellung von automobildecklackierungen
US5286782A (en) * 1992-08-31 1994-02-15 E. I. Du Pont De Nemours And Company Coating composition of an acrylic polymer, polyol and polyisocyanate crosslinking agent
DE4317861C1 (de) * 1993-05-28 1994-11-24 Herberts Gmbh Verfahren zur Mehrschichtlackierung von Substraten und Anwendung des Verfahrens
DE19622878A1 (de) * 1996-06-07 1997-12-11 Basf Lacke & Farben Mehrschichtige Lackierung, Verfahren zu deren Herstellung und hierfür geeigneter nicht-wäßriger Decklack
DE19704020A1 (de) * 1997-02-04 1998-08-06 Herberts Gmbh Hydroxylgruppenhaltige Copolymerisate und Verfahren zu ihrer Herstellung
WO1999003905A1 (fr) 1997-07-16 1999-01-28 E.I. Du Pont De Nemours And Company Emulsions de copolymere greffe et revetements d'urethanne a base aqueuse en deux paquets
US6780908B1 (en) * 2000-06-21 2004-08-24 E. I. Du Pont De Nemours And Company Coating composition
US6326059B1 (en) 2000-08-07 2001-12-04 E.I. Du Pont De Nemours And Company Two-stage cure coating compositions
US7001981B2 (en) 2003-04-25 2006-02-21 Sun Chemical Corporation Acrylated natural resins
CN109677332B (zh) * 2018-12-24 2022-06-28 惠州建邦精密塑胶有限公司 金属外观弹性汽车装饰件
KR20210142618A (ko) * 2019-03-18 2021-11-25 알넥스 네덜란드 비. 브이. 비수성 가교성 조성물
CN114127209B (zh) 2019-07-31 2023-08-15 巴斯夫涂料有限公司 用于生产具有低voc的水性涂料的混合体系
EP4004126B1 (fr) 2019-07-31 2023-09-06 BASF Coatings GmbH Système de mélange destiné à la fabrication d'agents de revêtement aqueux à faible part de cov
WO2022248282A1 (fr) 2021-05-28 2022-12-01 Basf Coatings Gmbh Système mélangeur pour produire des matériaux de revêtement aqueux
WO2023006474A1 (fr) 2021-07-26 2023-02-02 Basf Coatings Gmbh Système de revêtement pelable et procédés de formation du système de revêtement pelable

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE741519A (fr) * 1968-11-12 1970-05-11
DE2507884B2 (de) * 1975-02-24 1981-02-05 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung wäßriger Dispersionen von pigmentierten Überzugsmitteln
AT356226B (de) * 1977-10-24 1980-04-10 Vianova Kunstharz Ag Verfahren zur herstellung kathodisch ab- scheidbarer bindemittel
US4339365A (en) 1979-07-23 1982-07-13 Ppg Industries, Inc. Coating compositions containing pigment dispersants
AT367436B (de) 1980-11-13 1982-07-12 Vianova Kunstharz Ag Verfahren zur herstellung von copolymerisaten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8902452A1 *

Also Published As

Publication number Publication date
DE3731652A1 (de) 1989-04-06
EP0308756A1 (fr) 1989-03-29
WO1989002452A1 (fr) 1989-03-23
BR8807707A (pt) 1990-07-31
ATE78272T1 (de) 1992-08-15
EP0308756B1 (fr) 1992-07-15
ES2042669T3 (es) 1993-12-16
DE3872813D1 (de) 1992-08-20

Similar Documents

Publication Publication Date Title
EP0506703B1 (fr) Copolymerisats solubles reticulables a base de monomeres d'esters vinyliques, aromatiques-vinyliques et d'acrylate, leur procede de fabrication et leur utilisation dans les agents de revetement
EP0484356B1 (fr) Enduit a base de polymeres contenant des groupes carboxyles et d'agents de reticulation contenant des groupes epoxydes, son procede de fabrication ainsi que son application
EP0308756B1 (fr) Matière de revêtement à base d'un polymérisat d'acrylate ayant des groupes hydroxy, carboxyle et aminotertiaires, procédé de préparation de la matière de revêtement et son utilisation
EP0349818B1 (fr) Copolymères contenant des groupes hydroxyl à base de monomères d'esters vinyliques, de monomères vinylaromatiques et de monomères d'esters hydroxylalcoyl, procédé de leur préparation et leur usage dans des compositions de revêtement
WO1994022969A1 (fr) Procede d'application d'une double couche de laque de finition sur la surface d'un substrat
EP0605481A1 (fr) Peintures aqueuses et procede pour la fabrication de vernis de finition pour automobiles.
EP0044393A2 (fr) Procédé de préparation d'une résine (méth)acrylique modifiée par l'epsilon-caprolactone et contenant des groupes hydroxyles
EP0856533A1 (fr) Polymères contenant des groupes hydroxyl et un procédé pour leur préparation
DE4407409A1 (de) Beschichtungsmittel auf Basis eines hydroxylgruppenhaltigen Polyacrylatharzes und seine Verwendung in Verfahren zur Herstellung einer Mehrschichtlackierung
EP0320719B1 (fr) Liant, procédé pour sa préparation et son utilisation dans des revêtements clairs ou colorés
EP0242513A1 (fr) Revêtement à base d'un copolymère d'acrylate à groupes hydroxyles, carboxyliques et amino tertiaires, procédé de préparation du revêtement et son utilisation
EP0361048B1 (fr) Compositions durcissables à base d'un produit d'addition de "Michael", leur préparation et leur utilisation
DE602004001354T2 (de) Zweikomponenten-Beschichtungszusammensetzungen
EP0475981B1 (fr) Copolymeres contenant des groupes carboxyle et eventuellement des groupes tertiaires amino, leur procede de production et leur utilisation comme matieres d'enduction
EP0000608A1 (fr) Procédé pour la préparation de copolymères contenant des groupes hydroxyles, solubles dans les solvants organiques, ainsi que compositions de revêtement et liants pour laques
EP0621808B1 (fr) Procede de fabrication d'un revetement de vernis multicouche, vernis non aqueux et resines de polyacrylate autoreticulables
EP0355408B1 (fr) Copolymères contenant de groupes amino, leur procédé de préparation et leur application aux revêtements
EP0656924B1 (fr) Procede d'application de plusieurs couches de laque sur un substrat
DE102016105721B4 (de) Acrylpolymere, 1K-Beschichtungszusammensetzungen, die dieselben einschließen, und Mehrschichtbeschichtungssysteme, die eine Decklackschicht einschließen, die aus den 1K-Beschichtungszusammensetzungen gebildet wird
EP0625529B1 (fr) Mélange de liants et son utilisation
DE2851613A1 (de) Verfahren zur herstellung von in organischen loesungsmitteln loeslichen hydroxylgruppentragenden copolymerisaten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 19900203

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

XX Miscellaneous (additional remarks)

Free format text: VERFAHREN ABGESCHLOSSEN INFOLGE VERBINDUNG MIT 88114851.4/0308756 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) VOM 05.07.91.