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EP0441800A1 - Procede de fabrication d'un revetement multicouches - Google Patents

Procede de fabrication d'un revetement multicouches

Info

Publication number
EP0441800A1
EP0441800A1 EP89911034A EP89911034A EP0441800A1 EP 0441800 A1 EP0441800 A1 EP 0441800A1 EP 89911034 A EP89911034 A EP 89911034A EP 89911034 A EP89911034 A EP 89911034A EP 0441800 A1 EP0441800 A1 EP 0441800A1
Authority
EP
European Patent Office
Prior art keywords
weight
mixture
component
copolymerizable
monomers
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
EP89911034A
Other languages
German (de)
English (en)
Inventor
Stephan Schwarte
Ulrich Poth
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6364952&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0441800(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF Lacke und Farben AG filed Critical BASF Lacke und Farben AG
Publication of EP0441800A1 publication Critical patent/EP0441800A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers

Definitions

  • the invention relates to a method for producing a multilayer protective and / or decorative coating on a substrate surface, in which
  • a suitable pigmented basecoat composition is applied to the substrate surface.
  • the invention also relates to aqueous coating compositions, water-thinnable polyacrylate resins and a process for producing water-thinnable polyacrylate resins. resin.
  • the method according to the preamble of claim 1 is known. It is used in particular for the production of automotive metal effect coatings (see, for example, US-A-3,639,147, DE-A-33 33 072 and EP-A-38127).
  • aqueous top coating compositions for economic and ecological reasons, it is desirable to use aqueous top coating compositions in stage (3) of the so-called “base coat-clear coat” process described above.
  • top coating compositions must be sprayable using automatic painting equipment. For this purpose, they have to have such a high solids content at spray viscosity that lacquer films with a sufficient layer thickness are obtained with one to two spray coats (cross coats), and they have to deliver baked lacquer films which have a good appearance (good flow, high gloss, good) Topcoat level ...) show.
  • the aqueous top coating composition disclosed in Example 2 of EP-A-38127 does not meet all of the above requirements.
  • the task on which the present invention is based consists in the provision of aqueous top coating compositions which meet the above-mentioned requirements.
  • top coating compositions which contain a water-dilutable polyacrylate resin as a binder, which is obtainable by (I)
  • (b2) an ethylenically unsaturated monomer copolymerizable with (b1), (b3), (al) and (a2), which carries at least one hydroxyl group per molecule and is essentially free of carboxyl groups or a mixture of such monomers and if necessary
  • (b3) a copolymerizable with (b1), (b2), (a1) and (a2), essentially carboxyl-free ethylenically unsaturated monomers or a mixture of such monomers
  • Polyacrylate resin is at least partially neutralized and dispersed in water, the sum of the weight fractions of (al) and (a2) always giving 100% by weight and (bl), (b2), (b3), (al) and (a2) be selected in type and amount so that the polyacrylate resin has a hydroxyl number of 40 to 200, preferably 60 to 140, an acid number of 20 to 100, preferably 25 to 50 and a glass transition temperature (T_) of -40 ° C to + 60 ° C, preferably -20 ° C to + 40 ° C, has.
  • T_ glass transition temperature
  • the pigmented base coating compositions to be applied in stage (1) of the process according to the invention are well known (cf. e.g. US-A-3,639,147, EP-A-38127, DE-A-33 33 072 and EP-A-279 813).
  • base coating compositions containing metal pigments, in particular aluminum pigments are preferably used. In this way, metallic effect coatings are obtained.
  • component (a1) can be any ethylenically unsaturated monomer which carries at least one carboxyl group per molecule and can be copolymerized with (b1), (b2) and (b3) or a mixture of such monomers.
  • Acrylic acid and / or methacrylic acid are preferably used as component (a1).
  • other ethylenically unsaturated acids with up to 6 carbon atoms in the molecule can also be used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
  • component (al) e.g. succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester can also be used.
  • Component (a2) can be any ethylenically unsaturated monomer copolymerizable with (bl), (b2), (b3) and (al) or a mixture of such monomers. All monomers listed in the description of components (b1), (b2) and (b3) can be used as component (a2).
  • component (al) it is preferred to use 100% by weight of component (al). In other words: it is preferred to use component (a1) without admixing component (a2).
  • Component (bl) can be any of those which are copolymerizable with (b2), (b3), (al) and (a2) and are essentially free of carboxyl groups
  • Esters of (meth) acrylic acid or a mixture of such (meth) acrylic acid esters can be used.
  • Examples include alkyl acrylates and alkyl methacrylates with up to 20 carbon atoms in the alkyl radical, such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate .
  • alkyl acrylates and / or alkyl methacrylates are preferably used as (b1) components which consist of at least 25% by weight of n-butyl or t-butyl acrylate and / or n-butyl or t-butyl methacrylate.
  • component (b2) all ethylenically unsaturated monomers which can be copolymerized with (bl), (b3), (al) and (a2) and which carry at least one hydroxyl group per molecule and are essentially free from carboxyl groups, or a mixture of such monomers can be used .
  • Hydroxyalkyl esters of acrylic acid, methacrylic acid or another “ ⁇ , ß-ethylenically unsaturated carboxylic acid are mentioned as examples. These esters can be derived from an alkylene glycol which is esterified with the acid, or they can be obtained by reacting the acid with an alkylene oxide.
  • hydroxylalkyl esters of acrylic acid and methacrylic acid in which the hydroxyalkyl group contains up to 4 carbon atoms, reaction products of cyclic esters, such as, for example, £ -caprolactone and these hydroxyalkyl esters or mixtures of these hydroxyalkyl esters or Caprolactone-modified hydroxyalkyl esters are used.
  • hydroxyalkyl esters examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate.
  • esters of other unsaturated acids such as ethacrylic acid, crotonic acid and similar acids with up to about 6 carbon atoms per molecule can also be used.
  • Component (b3) which can be used is all copolymerizable with (b1), (b2), (a1) and (a2), essentially carboxyl-free ethylenically unsaturated monomers or mixtures of such monomers.
  • Vinylaromatic hydrocarbons such as styrene, (-alkylstyrene and vinyltoluene) are preferably used as component (b3).
  • the polyacrylate resins used according to the invention can be prepared by adding 60 to 100% by weight of component (a1) together with 0-40% by weight of component (a2) to an organic solvent or solvent mixture, at least there in the presence of a polymerization initiator and after the addition of components (a1) and (a2) has ended, a mixture (b) consisting of components (b1), (b2) and optionally (b3) to the organic solvent or solvent mixture is given and is polymerized there in the presence of at least one polymerization initiator. After the end of the polymerization, the polyacrylate resin obtained is at least partially neutralized and dispersed in water. The sum of the parts by weight of (al) and (a2) is always
  • the components (a1), (a2), (b1), (b2) and (b3) are selected in their type and amount so that the polyacrylate resin has a hydroxyl number of 40 to 200, preferably 60 to 140, an acid number of 20 to 100, preferably 25 to 50 and a glass transition temperature (T Q ) of -40 ° C to +60 ⁇ C, preferably -20 ° C to + 40 ° C.
  • Component (a1) - optionally together with component (a2) - is preferably added within 10 to 60 minutes, particularly preferably within 15 to 45 minutes added to the organic solvent or solvent mixture and polymerized there in the presence of at least one free radical-forming initiator.
  • Mixture (b) is preferably added to the organic solvent or solvent mixture within 2 to 8 hours, particularly preferably within 3 to 6 hours, and is polymerized there in the presence of at least one free radical initiator.
  • the polyacrylate resins to be used according to the invention can also be prepared by adding component (al) (optionally together with a2) and mixture (b) alternately to an organic solvent or solvent mixture and there in the presence of at least one free radical initiator are polymerized.
  • the partial amounts should each consist of at least 10% by weight of the total amount of component (a1) and (a2) or mixture (b) to be used.
  • the polyacrylate resin obtained is at least partially neutralized and dispersed in water. The sum of the parts by weight of (a1) and (a2) is always 100% by weight.
  • the components (a1), (a2), (b1), (b2) and (b3) are selected in their type and amount so that the polyacrylate resin has a hydroxyl number of 40 to 200, preferably 60 to 140, an acid number of 20 to 100, preferably 25 to 50 and a glass transition temperature (T G ) of -40 ° C to + 60 ° C, preferably -20 ⁇ C to + 40 ° C.
  • a first step one of 30 to 70% by weight, preferably one of 40 to 60% by weight, particularly preferably one of 50% by weight of the total amount of component ( b) existing subset of component (b) (subset 1) to the organic solvent or Given solvent mixture and polymerized in the presence of at least one free radical initiator.
  • a second step one of 30 to 70% by weight, preferably one of 40 to 60% by weight, particularly preferably one of 50% by weight of the total amount of component to be used (al) existing portion of component (al) (portion 2) added to the organic solvent or solvent mixture and polymerized in the presence of at least one free radical initiator.
  • portion 2 in a third step one of 30 to 70% by weight, preferably one of 40 to 60% by weight, particularly preferably one of 50% by weight of the total amount of component (b ) existing subset of component (b)
  • portion 4 consisting of 50% by weight of the total amount of component (a1) to be added to the organic solvent or solvent mixture and mixed in at least one free radical initiator is polymerized.
  • the polyacrylate resin obtained is at least partially neutralized and dispersed in water.
  • the sum of the parts by weight of (a1) and (a2) is always 100% by weight.
  • the components (a1), (a2), (b1), (b2) and (b3) are selected in their type and amount so that the polyacrylate resin has a hydroxyl number of 40 to 200, preferably 60 to 140, an acid number of 20 to 100, preferably 25 to 50 and a glass transition temperature (T Q ) of -40 ° C to + 60 ° C, preferably -20 ⁇ C to + 40 ° C.
  • the aliquots 1 and 3 are preferably added within 1 to 4 hours, particularly preferably within 1 1/2 to 3 hours.
  • the aliquots 2 and 4 are preferably added within 5 to 30 minutes, particularly preferably within 7 to 20 minutes.
  • the organic solvents and polymerization initiators used are the solvents and polymerization initiators customary for the production of polyacrylate resins and suitable for the production of aqueous dispersions.
  • useful solvents are butyl glycol, 2-methoxypropanol, n-butanol, methoxybutanol, n-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether Called -3-methoxybutanol.
  • Free radical-forming initiators such as e.g. Benzoyl peroxide, azobisisobutyronitrile and t-butyl perbenzoate called.
  • the polymerization is carried out at a temperature of 80 to 160 ° C, preferably 120 to 160 ° C. The polymerization is complete when essentially all of the monomers used have been reacted.
  • the components (a1), (a2), (b1), (b2) and (b3) are selected in their type and amount such that the reaction product has a hydroxyl number of 40 to 200, preferably 60 to 140, an acid number of 20 to 100 , preferably 25 to 50 and a glass transition temperature (T-,) of -40 ° C to + 60 ° C, preferably shows -20 ° C to + 40 ° C.
  • the glass transition temperatures of polyacrylate resins can be calculated approximately using the following formula:
  • the amount and rate of addition of the initiator is preferably controlled so that the polyacrylate resin obtained has a number average molecular weight of 2500 to 20,000. It is particularly preferred to start the initiator addition at the same time as the addition of the polymerizable components (al), (a2) and (b) and about half an hour after the addition of the polymerizable components (al), (a2) and (b) has been terminated.
  • the reaction mixture is then kept at the polymerization temperature (generally about 1 1/2 hours) until all of the monomers used have essentially been completely reacted.
  • “Substantially completely converted” is intended to mean that preferably 100% by weight of the monomers used have been reacted, but that it is also possible for a low residual monomer content of at most up to 0.5% by weight.
  • the polyacrylate resins according to the invention are produced by adding 40 to 87.5% by weight, preferably 55 to 80% by weight of component (b1), 10 to 45% by weight, preferably 12 to
  • component (b2) 35% by weight of component (b2), 0 to 25% by weight, preferably 8 to 18% by weight of component (b3), 2.5 to 15% by weight, preferably 3 to 7% by weight .-% of component (al) and 0 to 6 wt .-% of component (a2) are used, the sum of the parts by weight of (bl), (b2), (b3), (al) and (a2) always 100 wt .-% results.
  • the polyacrylate resin obtained is at least partially neutralized and dispersed in water.
  • Both organic bases and inorganic bases such as ammonia and hydrazine can be used for the neutralization.
  • Primary, secondary and tertiary amines e.g. Ethylamine, propylamine, diethylamine, dibutylamine, cyclohexylamine, benzylamine, morpholine, piperidine and triethanolamine are used.
  • Tertiary amines are particularly preferably used as neutralizing agents, in particular dimethylethanolamine, triethylamine, tripropylamine and tributylamine.
  • the neutralization reaction is generally carried out by mixing the neutralizing base with the polyacrylate resin.
  • the amount of base used is preferably such that the top coating composition has a pH of 7-8.5, preferably 7.2 to 7.8.
  • the partially or completely neutralized polyacrylate resin is then dispersed by adding water. This creates an aqueous polyacrylate resin dispersion. If necessary, some or all of the organic solvent be distilled off medium.
  • the polyacrylate resin dispersions according to the invention contain polyacrylate resin particles, the average particle size of which is preferably between 60 and 250 nm (measurement method: laser light scattering, measuring device: Malvern Autosizer 2C).
  • aqueous polyacrylate resin dispersions obtained in this way are prepared by admixing an aminoplast resin and, if appropriate, other additives, such as e.g. Leveling aids, UV stabilizers, transparent pigments, etc. are given top coating compositions according to the invention.
  • top coating compositions according to the invention preferably contain so much aminoplast resin that the weight ratio between polyacrylate resin solid and aminoplast resin solid is 60:40 to 90:10, particularly preferably 70:30 to 85:15.
  • all aminoplast resins that can be processed into a stable top coating composition with the polyacrylate resin according to the invention can be used as crosslinking agents.
  • Melamine-formaldehyde resins which are partially or completely etherified with aliphatic alcohols, which preferably contain 1 to 4 carbon atoms per molecule, are preferably used as crosslinking agents.
  • top coating compositions according to the invention are preferred for spray viscosity (generally 20 to 40 sec. Run-out time from DIN cup 4 (DIN 53211 (1974))) and a pH of 7.0 to 8.5 ⁇ set to 7.2 to 7.8.
  • the top coating compositions of the invention are preferred for spray viscosity (generally 20 to 40 sec. Run-out time from DIN cup 4 (DIN 53211 (1974))) and a pH of 7.0 to 8.5 ⁇ set to 7.2 to 7.8.
  • organic cosolvents have a relatively low proportion of organic cosolvents (less than 35% by weight, based on the total solids content of binders and crosslinking agents).
  • top coating compositions according to the invention are used together with water-thinnable base coating compositions for the production of metallic effect coatings, then metallic effect coatings are obtained in which the transparent top layer adheres particularly well to the base layer.
  • the top coating compositions according to the invention can also contain crosslinked polymer microparticles, such as are disclosed, for example, in EP-A-38127 and / or other compatible resins such as water-dilutable or water-soluble polyacrylate resins, polyester resins, alkyd resins or epoxy resin esters included, and they can also be pigmented.
  • crosslinked polymer microparticles such as are disclosed, for example, in EP-A-38127 and / or other compatible resins such as water-dilutable or water-soluble polyacrylate resins, polyester resins, alkyd resins or epoxy resin esters included, and they can also be pigmented.
  • Pl> 20 parts by weight of butyl glycol are placed in a 4 1 steel kettle equipped with two monomer feeds, an initiator feed, stirrer, thermometer, oil heater and reflux condenser and heated to 140 ° C. Then a solution of 4.5 parts by weight of butyl perbenzoate in 5 parts by weight of butyl glycol were added at such a rate that the addition of 4 h, 30 min was completed. With the beginning of the addition of the butyl perbenzoate solution, the addition of component (a1) is also started (cf. Table 1). Component (a1) is added at a rate such that the addition is complete after 20 minutes.
  • P2 20 parts by weight of butylglycol are placed in a 4 1 steel kettle equipped with two monomer feeds, an initiator feed, stirrer, thermometer, oil heating and reflux condenser and heated to 140.degree.
  • a solution of 4.5 parts by weight of butyl perbenzoate in 5 parts by weight of butyl glycol is then added at such a rate that the addition is complete after 4 hours and 30 minutes.
  • the resin solution thus obtained is neutralized with dimethylethanolamine at 95 ° C. to a degree of neutralization of 80%. Sufficient water is then added so that the solids content of the dispersion is about 60% by weight.
  • P3J inlets equipped with two monomer into a 4 1 steel vessel, an initiator inlet, stirrer, thermometer, oil heating and reflux condenser are placed 20 parts by weight Butyl ⁇ glycol and heated to 140 C ⁇ . Then a solution of 4.5 parts by weight of butyl perbenzoate in 5 parts by weight of butyl glycol is added at such a rate that the addition after 4 h, 30 min. is completed. At the beginning of the addition of the butyl perbenzoate solution, the addition of 33.3% by weight of the total amount of component (al) (partial amount 1) to be used is also started. The portion 1 is added at such a rate that the addition is complete after 10 minutes.
  • Partial amount 1 becomes 50% by weight of the total amount of the mixture of (bl), (b2) and (b3) (partial amount 2) to be used within 1 hour, 55 minutes. admitted.
  • 33.3% by weight of the total amount of component (al) (partial amount 3) to be used are added within 10 minutes.
  • portion 3 the remaining 50% by weight of the total amount of the mixture of (bl), (b2) and (b3) (portion 4) to be used are added within 1 h, 55 min.
  • portion 4 the remaining 33.33% by weight of the total amount of component (al) (portion 5) to be used is finally added within 10 minutes.
  • the reaction mixture is then kept at 140 ° C. until the solids content of the resin solution is at least 80% by weight (1 h, 130 ° C.).
  • the resin solution thus obtained is neutralized with dimethylethanolamine at 95 ° C. to a degree of neutralization of 80%. Sufficient water is then added so that the solids content of the dispersion is about 60% by weight.
  • topcoat compositions are prepared and sprayed with a 10% aqueous dimethylethanolamine solution and distilled water (24 s run-out time from DIN cup 4 (DIN 53211 (1974))) and a pH of 7.4 to 7.5.
  • the top coat Processing compositions contain 20% by weight of organic cosolvents, based on the total solids content of polyacrylate resin and melamine-formaldehyde resin.
  • the applied base coating composition is 10 min. at room temperature and 10 min. getrock ⁇ net at 80 ° C.
  • a top coating composition obtained in accordance with point B is then sprayed onto the base layer in two cloisters with an intermediate flash-off time of one minute.
  • the multilayer coatings obtained in this way were subjected to several tests. The test results are summarized in the following table:
  • the monomers (al), (bl), (b2) and (b3) used to prepare the polyacrylate resins P1 and P3 according to the invention are mixed and polymerized.
  • the polymerization conditions are the same as in the production of the polyacrylate resins P1 and P3 according to the invention.
  • component (a1) does not precede the mixture of (bl), (b2) and (b3) as in Pl and does not alternate as in P3, but instead is added together with (bl), (b2) and (b3).
  • An aqueous top coating composition prepared from the polyacrylate resin V according to B prepared in this way has a viscosity of 24 DIN seconds (run-out time from DIN cup 4 (DIN 53211 (1974))) and a pH of 7.4 to 7 , 5 only has a solids content of 24.1% by weight.
  • the following diagram shows the viscosities of the polyacrylate dispersions P1 and P3 prepared according to A and diluted with water as a function of the solids content of the dispersions in comparison to an analogous dispersion of the polyacrylate resin V (pH value of the dispersions: 7.8). It is clear that the viscosities of the polyacrylate resin dispersions P1 and P3 at solids contents of 25 to about 53% by weight are lower than the viscosity of the dispersion of the polyacrylate resin V.
  • FK solids content in 6% by weight

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Procédé de fabrication d'un revêtement multicouches à base d'un composé de revêtement de protection dont le liant est une résine polyacrylique. On obtient cette dernière en ajoutant à un solvant organique, soit l'un après l'autre, soit en plus petites quantités alternées, les produits suivants: (a1) un monomère éthylénique non saturé contenant des groupes carboxyle et (b) un mélange d'esters d'acide (méth)acrylique sans groupes carboxyliques et de monomères éthyléniques non saturés contenant des groupes hydroxy; on polymérise ensuite ces produits en présence d'un excitant formant des radicaux et, une fois la polymérisation terminée, on neutralise la résine polyacrylique qui en résulte et on la disperse dans de l'eau. On choisit le type et la quantité des produits (a1) et (b) de manière à ce que la résine polyacrylique ait un indice hydroxy de 40 à 200, un indice d'acidité de 20 à 100 et une température de transition vitreuse (TG) de -40°C à +60°C.
EP89911034A 1988-10-12 1989-09-26 Procede de fabrication d'un revetement multicouches Pending EP0441800A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3834738A DE3834738A1 (de) 1988-10-12 1988-10-12 Verfahren zur herstellung eines mehrschichtigen ueberzuges, waessrige beschichtungszusammensetzungen, wasserverduennbare polyacrylatharze und verfahren zur herstellung von wasserverduennbaren polyacrylatharzen
DE3834738 1988-10-12

Publications (1)

Publication Number Publication Date
EP0441800A1 true EP0441800A1 (fr) 1991-08-21

Family

ID=6364952

Family Applications (2)

Application Number Title Priority Date Filing Date
EP19890117746 Expired - Lifetime EP0363723B1 (fr) 1988-10-12 1989-09-26 Procédé de préparation d'un revêtement multicouche, compositions de revêtement aqueuses, résines acryliques diluables dans l'eau et procédé de préparation de résines acryliques diluables dans l'eau
EP89911034A Pending EP0441800A1 (fr) 1988-10-12 1989-09-26 Procede de fabrication d'un revetement multicouches

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP19890117746 Expired - Lifetime EP0363723B1 (fr) 1988-10-12 1989-09-26 Procédé de préparation d'un revêtement multicouche, compositions de revêtement aqueuses, résines acryliques diluables dans l'eau et procédé de préparation de résines acryliques diluables dans l'eau

Country Status (11)

Country Link
US (1) US5266361A (fr)
EP (2) EP0363723B1 (fr)
JP (1) JPH072929B2 (fr)
AT (1) ATE77976T1 (fr)
AU (1) AU625803B2 (fr)
BR (1) BR8907720A (fr)
CA (1) CA1340621C (fr)
DE (2) DE3834738A1 (fr)
ES (1) ES2033505T3 (fr)
WO (1) WO1990003851A1 (fr)
ZA (1) ZA897581B (fr)

Families Citing this family (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4009858C2 (de) * 1990-03-28 1998-02-05 Basf Lacke & Farben Wäßriger pigmentierter Basislack enthaltend als Bindemittel ein wasserverdünnbares Polyacrylatharz und Verwendung eines solchen Basislacks
JP2882730B2 (ja) * 1993-07-13 1999-04-12 三菱レイヨン株式会社 水性被覆用組成物
DE4413562A1 (de) * 1994-04-19 1995-10-26 Herberts Gmbh Wäßrige Dispersion von Siloxanbrücken enthaltenden Polyurethanen, deren Herstellung und Verwendung in Überzugsmitteln
US5691002A (en) * 1994-06-03 1997-11-25 Kansai Paint Company, Limited. Coating method
US5807494A (en) 1994-12-15 1998-09-15 Boes; Ralph Ulrich Gel compositions comprising silica and functionalized carbon products
IL116378A (en) 1994-12-15 2003-05-29 Cabot Corp Non-aqueous coating or ink composition with improved optical properties containing modified carbon product and method of preparation of the composition
IL154538A (en) 1994-12-15 2009-12-24 Cabot Corp The reaction of carbon black with diazonium salts, the resulting carbon black products
US5554739A (en) 1994-12-15 1996-09-10 Cabot Corporation Process for preparing carbon materials with diazonium salts and resultant carbon products
US5559169A (en) 1994-12-15 1996-09-24 Cabot Corporation EPDM, HNBR and Butyl rubber compositions containing carbon black products
IL116376A (en) 1994-12-15 2001-03-19 Cabot Corp Aqueous ink jet ink compositions containing modified carbon products
US5571311A (en) 1994-12-15 1996-11-05 Cabot Corporation Ink jet ink formulations containing carbon black products
IL116379A (en) 1994-12-15 2003-12-10 Cabot Corp Aqueous inks and coatings containing modified carbon products
US5575845A (en) 1994-12-15 1996-11-19 Cabot Corporation Carbon black products for coloring mineral binders
US6028137A (en) 1995-05-22 2000-02-22 Cabot Corporation Elastomeric compounds incorporating silicon-treated carbon blacks
US5622557A (en) 1995-05-22 1997-04-22 Cabot Corporation Mineral binders colored with silicon-containing carbon black
US6323273B1 (en) 1995-05-22 2001-11-27 Cabot Corporation Elastomeric compounds incorporating silicon-treated carbon blacks
JP3305722B2 (ja) 1995-05-22 2002-07-24 キャボット コーポレイション 部分的に被覆されたカーボンブラックを含有するエラストマーのコンパウンド
US5773513A (en) * 1996-04-04 1998-06-30 E. I. Du Pont De Nemours And Company Hydroxy functional acrylic polymer prepared via skew feed polymerization
US5958999A (en) 1996-04-05 1999-09-28 Cabot Corporation Ink compositions and method for generating images produced therefrom
US5747562A (en) 1996-06-14 1998-05-05 Cabot Corporation Ink and coating compositions containing silicon-treated carbon black
US5707432A (en) 1996-06-14 1998-01-13 Cabot Corporation Modified carbon products and inks and coatings containing modified carbon products
US5698016A (en) 1996-06-14 1997-12-16 Cabot Corporation Compositions of modified carbon products and amphiphilic ions and methods of using the same
EP0909212B1 (fr) 1996-06-14 2012-02-01 Cabot Corporation Utilisation et Procédé d'utilisation d' adsorbants carbones modifies
EP0844217B1 (fr) * 1996-11-21 2001-06-20 Mitsuboshi Belting Ltd. Couche colorée et cuite, et procédé pour la fabrication
US5919855A (en) 1997-02-11 1999-07-06 Cabot Corporation Use of modified carbon black in gas-phase polymerizations
KR20010021919A (ko) 1997-07-16 2001-03-15 메리 이. 보울러 그래프트 공중합체 에멀젼 및 2 팩키지형 수계 우레탄코팅물
EP2316875A1 (fr) 1999-01-20 2011-05-04 Cabot Corporation Agrégats dotés de groupes polymères attachés et mousses de polymère
AU3210800A (en) 1999-01-20 2000-08-07 Cabot Corporation Aggregates having attached polymer groups and polymer foams
DE19903391A1 (de) 1999-01-29 2000-08-03 Bayer Ag Wäßriges Überzugsmittel, Verfahren zu seiner Herstellung und seine Verwendung
DE19930066A1 (de) * 1999-06-30 2001-01-11 Basf Coatings Ag Farb- und/oder effektgebende Mehrschichtlackierung, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2001025340A1 (fr) 1999-10-01 2001-04-12 Cabot Corporation Pigments modifies comportant des groupes steriques et amphiphiles
AU1353501A (en) 1999-10-28 2001-05-08 Cabot Corporation Ink jet inks, inks, and other compositions containing colored pigments
ATE519822T1 (de) 1999-10-28 2011-08-15 Cabot Corp Tintenstrahltinten, tinten, sowie andere zusammensetzungen enthaltend farbige pigmente
US6391973B1 (en) 2000-07-24 2002-05-21 Basf Corporation Curable coating composition with improved stability
DE10237194A1 (de) * 2002-08-14 2004-02-26 Bayer Ag Wasserverdünnbare Polyester mit cyclischer Imidstruktur (I)
DE10237195A1 (de) 2002-08-14 2004-02-26 Bayer Ag Wasserverdünnbare Polyester mit cyclischer Imid- und Isocyanuratstruktur
DE102005050823A1 (de) * 2005-10-24 2007-04-26 Basf Coatings Ag Von organischen Lösemitteln im Wesentlichen oder völlig freie, strukturviskose, härtbare, wässrige Pulverdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
MX2009004828A (es) * 2006-11-07 2009-08-24 Cabot Corp Negros de carbon que tienen bajas cantidades de pah y métodos para su elaboración.
WO2012074868A2 (fr) 2010-12-03 2012-06-07 Ms Technologies, Llc Expression optimisée de molécules d'acide nucléique codant pour la résistance au glyphosate dans cellules végétales
EP3705538B1 (fr) 2010-12-14 2021-04-28 Cabot Corporation Compositions charge-polymère comprenant un polymère de silicone et une charge à deux phases ayant une phase de silice et une phase de carbone
US8648230B2 (en) 2011-03-18 2014-02-11 Ms Technologies, Llc Regulatory regions preferentially expressing in non-pollen plant tissue
AR090418A1 (es) 2012-02-01 2014-11-12 Dow Agrosciences Llc Peptido de transito al cloroplasto
US9175150B2 (en) 2012-03-02 2015-11-03 Cabot Corporation Modified carbon blacks having low PAH amounts and elastomers containing the same
KR101772783B1 (ko) 2013-03-13 2017-08-29 캐보트 코포레이션 조합된 낮은 유전 상수, 높은 비저항, 및 광학 밀도 특성, 및 제어된 전기 비저항을 갖는 충전제-중합체 조성물을 갖는 코팅, 및 그로 제조된 장치, 및 그의 제조 방법
EP3065540B1 (fr) 2013-11-04 2021-12-15 Corteva Agriscience LLC Loci optimaux de maïs
UA120503C2 (uk) 2013-11-04 2019-12-26 Дау Агросайєнсиз Елелсі Спосіб одержання трансгенної клітини рослини кукурудзи
NZ746567A (en) 2013-11-04 2019-09-27 Dow Agrosciences Llc Optimal soybean loci
TW201527314A (zh) 2013-12-31 2015-07-16 Dow Agrosciences Llc 新穎玉米泛素啓動子（三）
TW201527316A (zh) 2013-12-31 2015-07-16 Dow Agrosciences Llc 新穎玉米泛素啓動子（五）
TW201527312A (zh) 2013-12-31 2015-07-16 Dow Agrosciences Llc 新穎玉米泛素啓動子（一）
TW201527313A (zh) 2013-12-31 2015-07-16 Dow Agrosciences Llc 新穎玉米泛素啓動子（二）
TW201538518A (zh) 2014-02-28 2015-10-16 Dow Agrosciences Llc 藉由嵌合基因調控元件所賦予之根部特異性表現

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1284755A (en) 1968-09-30 1972-08-09 Celanese Coatings Co Process for coating surfaces and compositions for use therein
DE2850872A1 (de) * 1978-11-24 1980-06-04 Bayer Ag Wasserverduennbare lackbindemittel fuer chemikalienfeste beschichtungen
DE2936518A1 (de) * 1979-09-10 1981-03-26 Cassella Ag, 60386 Frankfurt Lagerstabiles acrylatmodifiziertes melaminharz, seine herstellung und verwendung
US4590235A (en) * 1979-09-28 1986-05-20 E. I. Du Pont De Nemours And Company Dual-layer coating containing aluminum-flake pigment and coated article
EP0038127B1 (fr) 1980-04-14 1984-10-17 Imperial Chemical Industries Plc Procédé pour enduire en plusieurs couches, comprenant l'utilisation d'une composition aqueuse à caractère thixotropique d'enduit de fond contenant des particules d'un polymère réticulé
JPS5740512A (en) 1980-08-25 1982-03-06 Sekisui Chem Co Ltd Production of water-dispersed resin
JPS5744674A (en) * 1980-08-29 1982-03-13 Nippon Paint Co Ltd Resin composition for coating material
US4598111A (en) * 1982-03-18 1986-07-01 Glasurit America, Inc. Coating composition containing cross-linked microparticles
US4450251A (en) * 1983-03-09 1984-05-22 Desoto, Inc. Thermosetting aqueous varnish compositions
US4546046A (en) * 1983-03-10 1985-10-08 Glasurit America, Inc. Substrates with flexible coatings from epsilon-caprolactone modified acrylics
DE3333072A1 (de) 1983-09-14 1985-03-21 Basf Farben + Fasern Ag, 2000 Hamburg Ueberzugsmasse, verfahren zur herstellung von ueberzuegen und beschichtetes substrat
DE3409080A1 (de) * 1984-03-13 1985-09-19 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von waessrigen dispersionen und deren verwendung zur herstellung von metalleffektlackierungen
DE3412534A1 (de) * 1984-04-04 1985-10-17 Basf Farben + Fasern Ag, 2000 Hamburg Durch saeure haertbare ueberzugsmittel und verfahren zu ihrer herstellung
JPS61143472A (ja) * 1984-12-17 1986-07-01 Mitsubishi Rayon Co Ltd 塗料用組成物
US4980410A (en) * 1985-05-10 1990-12-25 E. I. Du Pont De Nemours And Company Acrylic copolymer composition and adhesive coatings therefrom
US4591533A (en) * 1985-06-03 1986-05-27 E. I. Du Pont De Nemours And Company Coating composition of an acrylic polymer, a dispersed acrylic polymer and an alkylated melamine crosslinking agent
DE3543361A1 (de) 1985-12-07 1987-06-11 Basf Ag Verfahren zur herstellung waessriger polymerdispersionen und deren verwendung
DE3545618A1 (de) 1985-12-21 1987-06-25 Basf Lacke & Farben Wasserverduennbares ueberzugsmittel zur herstellung der basisschicht eines mehrschichtueberzuges
JPS62181367A (ja) * 1986-02-05 1987-08-08 Nippon Paint Co Ltd 樹脂分散型水性塗料組成物
US5077348A (en) * 1986-10-31 1991-12-31 Toyo Ink Manufacturing Co., Ltd. Aqueous coating composition, process for the production thereof and aqueous coating
JPH0759681B2 (ja) * 1987-02-06 1995-06-28 関西ペイント株式会社 水性被覆組成物
US4808656A (en) * 1987-05-04 1989-02-28 Ppg Industries, Inc. High solids coating compositions
JP2652159B2 (ja) * 1987-05-06 1997-09-10 三菱レイヨン株式会社 熱硬化被覆組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9003851A1 *

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WO1990003851A1 (fr) 1990-04-19
ZA897581B (en) 1990-07-25
EP0363723B1 (fr) 1992-07-08
CA1340621C (fr) 1999-06-29
JPH03504138A (ja) 1991-09-12
AU4335389A (en) 1990-05-01
ES2033505T3 (es) 1993-03-16
JPH072929B2 (ja) 1995-01-18
AU625803B2 (en) 1992-07-16
DE58901811D1 (de) 1992-08-13
BR8907720A (pt) 1991-07-30
DE3834738A1 (de) 1990-04-19
EP0363723A1 (fr) 1990-04-18
ATE77976T1 (de) 1992-07-15
US5266361A (en) 1993-11-30

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