EP0652911A1 - Composition de revetement en poudre avec agent de reticulation a base d'hydroxyalkylamide - Google Patents

Composition de revetement en poudre avec agent de reticulation a base d'hydroxyalkylamide

Info

Publication number
EP0652911A1
EP0652911A1 EP93918083A EP93918083A EP0652911A1 EP 0652911 A1 EP0652911 A1 EP 0652911A1 EP 93918083 A EP93918083 A EP 93918083A EP 93918083 A EP93918083 A EP 93918083A EP 0652911 A1 EP0652911 A1 EP 0652911A1
Authority
EP
European Patent Office
Prior art keywords
compound
hydroxyalkylamide
functionality
powder coating
crosslinker
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Withdrawn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
EP93918083A
Other languages
German (de)
English (en)
Inventor
Dirk Armand Wim Stanssens
Wilhelmus Henricus Hubertus Van Den Elshout
Marten Houweling
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.)
Koninklijke DSM NV
Original Assignee
DSM NV
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 DSM NV filed Critical DSM NV
Publication of EP0652911A1 publication Critical patent/EP0652911A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • the invention relates to a powder coating compostion comprising as a binder a polymer with free carboxylic acid groups and as a crosslinker a compound containing ⁇ -hydroxyalkylamide groups.
  • a powder coating comprising a co-reactable mixture of an amorphous carboxylic acid group containing polyester and a ⁇ -hydroxyalkylamide is known from EP-A- 322834.
  • the composition described in this application is cured - after application to a substrate - by heating the powder to 160-200°C so that the powder melts, forming a smooth layer. At that temperature the coating is chemically crosslinked due to an esterification reaction between the acid groups of the polymer and the hydroxy groups of the compound containing ⁇ -hydroxyalkylamide groups.
  • a de-gasifying agent benzoin (0.5 to 3% by wt. of the powder composition) may be added to the composition.
  • a de-gasifying agent is needed to ensure that the air and/or water entrapped due to melting of the powder (during a curing cycle) are removed from the paint layer as a result of the reaction. Any gas bubbles that remain in the coating reduce the adhesion of the coating to the substrate and markedly adversely affect the protection obtainable with the coating.
  • compositions are characterized in EP-A-322834 as having good physical properties, such compositions are unsuitable for preparing a white or crystal-clear coating because the powder coating exhibits some degree of browning after curing, as indicated in Mercurio, New Perspective on Hydroxyamide Crosslinkers, 16th International Conf. in Org. Sci. and Tech. 235-49 (Athens, Greece 1990).
  • browning appears to intensify upon heating the cured powder coating at a temperature of 200°C for a prolonged period of time (for example between 30 and 60 minutes). This discolouration upon excessive curing (yellowing on overbake) increases with the amount of benzoin. A lower amount of benzoin, on the other hand, results in a lower blister limit, such as lower than 60 ⁇ m, which results in surface defects.
  • the object of the invention is to provide a powder coating composition in which it is possible to use a small amount of benzoin, for example between 0.05 and 0.8 wt.%, to obtain the highest possible blister limit, for example higher than 120 ⁇ m.
  • the powder coatings must also retain good mechanical properties, such as, for example, good gloss, toughness and impact resistance and chemical properties such as for example a good chemical resistance.
  • the invention is characterized in that the crosslinker comprises a combination of at least two compounds containing ⁇ -hydroxyalkylamide groups and each compound having different ⁇ -hydroxylalkylamide functionalities, the first compound having a ⁇ -hydroxy ⁇ alkylamide functionality of . 3 and the second compound having a ⁇ -hydroxyalkylamide functionality of . 3.
  • the functionality stands for the average number of ⁇ -hydroxyalkylamide groups per molecule.
  • Suitable compounds containing ⁇ - hydroxyalkylamide groups and having a functionality of ⁇ 3 can be depicted structurally according to formula (I):
  • R 1 represents hydrogen, an alkyl group with 1- 5 carbon atoms (for example methyl, ethyl, n-propyl, n-butyl, sec. butyl, tert. butyl and pentyl) or a hydroxy- alkyl group with 1-5 carbon atoms (for example 2-hydroxy- ethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxy-2-methylpropyl, or the hydroxy derivatives of the pentyl isomers);
  • R 2 and R 3 are the same or different and each independently represents hydrogen or a straight or branched alkyl group with 1-5 carbon atoms, while one of the groups R 2 and one of the groups R 3 may also form, together with the adjacent carbon atoms, a cycloalkyl group, such as, for example, cyclopentyl and cyclohexyl; R 2 and R 3 may also be hydroxyalkyl groups, such as, for example, hydroxy (C 1 -C 5 )-alkyl groups, hydroxymethyl and 1-hydroxyethyl, being preferred among the latter and
  • A is an alkyl group with (1-10) carbon atoms
  • R 1 represents 2-hydroxyethyl or hydrogen
  • R 2 and R 3 are independent of one another hydrogen or hydroxy ( Ci-Cj J-alkyl .
  • the first compound having a ⁇ - hydroxyalkylamide functionality of ⁇ 3 is a compound according to formula (II):
  • Very suitable compounds having a ⁇ -hydroxyalkyl ⁇ amide functionality of ⁇ 3 are compounds according to formula (I) having a ⁇ -hydroxyalkylamide functionality of . 3 or compounds according to formula (III):
  • A is an alkyl group with (1-10) carbon atoms
  • R 1 represents 2-hydroxyethyl or hydrogen
  • R 2 and R 3 are independent of one another hydrogen or hydroxy (C 1 _C 2 )-alkyl.
  • the second compound having a ⁇ - hydroxyalkylamide functionality of r. 3 is a compound according to formula (IV):
  • the functionality of the second compound having a functionality of ⁇ 3 according to formula (I) is 2.
  • Compounds according to formula (V) are also very suitable as compounds having a functionality of _ 3:
  • the weight ratio in the crosslinker between is preferably between 90:10 and 10:90 and more preferably between 80:20 and 20:80. This ratio depends on the functionality of the polymer with free carboxylic groups.
  • the average functionality of the polymer is between 1.7 and 4.5 and preferably between 2.3 and 3.5.
  • the weight ratio of the crosslinker to the polymer is usually between 10:90 and 3:97, more preferably between 20:80 and 3:97.
  • the acid number of the polymer containing carboxyl groups is preferably between about 15 and about 150 mg KOH/gram resin, in particular is between about 20 and about 70 mg KOH/gram resin.
  • the glass transition temperature, Tg is preferably between about 30°C and about 80°C and in particular ranges between about 35°C and about 65°C.
  • the polymer that contains carboxyl groups is a polyester and/or a polyacrylate.
  • Examples of preferred monomers for polyacrylates that can be incorporated in the main chain of the polymer are unsaturated monocarboxylic acids, such as, for example, acrylic acid, methacrylic acid and crotonic acid, unsaturated dicarboxylic acids, such as, for example, maleic acid, 2-methyl maleic acid, itaconic acid, and ⁇ - ⁇ -methylene glutaric acid, unsaturated anhydrides, such as, for example, maleic anhydride, itaconic anhydride, acrylic anhydride and methacrylic anhydride.
  • unsaturated monocarboxylic acids such as, for example, acrylic acid, methacrylic acid and crotonic acid
  • unsaturated dicarboxylic acids such as, for example, maleic acid, 2-methyl maleic acid, itaconic acid, and ⁇ - ⁇ -methylene glutaric acid
  • unsaturated anhydrides such as, for example, maleic anhydride, itaconic anhydride, acrylic anhydride and methacrylic anhydr
  • the polymer usually also consists of copolymerized esters of (meth)acrylic acid, such as, for example, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate or acrylonitrile, styrene and other ethylenically unsaturated compounds.
  • (meth)acrylic acid such as, for example, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate or acrylonitrile, styrene and other ethylenically unsaturated compounds.
  • Suitable polyesters can be obtained via standard preparation methods from essentially aromatic poly- carboxylic acids, such as, for example, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 3,6-dichloro phthalic acid, tetrachloro phthalic acid, or, if obtainable, the anhydrides, acid chlorides or lower alkyl esters thereof.
  • carboxylic acid component is composed at least of 50% by weight, preferably at least 70 mol %, of isophthalic acid and/or terephthalic acid. Exemplary procedures are described in said reference of Misev at pages 144-162.
  • the polycarboxylic acids used can also be cyclo- aliphatic and/or acyclic polycarboxylic acids such as, for example, tetrahydro phthalic acid, hexahydro-endomethylene terephthalic acid, hexachloro tetrahydrophthalic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, dimer fatty acid, adipic acid, succinic acid and maleic acid, in amounts of up to not more than 30 mol%, preferably up to not more than 20 mol%, of the total of carboxylic acids.
  • cyclo- aliphatic and/or acyclic polycarboxylic acids such as, for example, tetrahydro phthalic acid, hexahydro-endomethylene terephthalic acid, hexachloro tetrahydrophthalic acid, azelaic acid, sebacic acid, decane dicarboxylic acid,
  • Hydroxy-carboxylic acids and/or, optionally, lactones such as, for example, 12-hydroxy- stearic acid, ⁇ -caprolactone and the hydroxypivalic acid ester of neopentyl glycol can also be used.
  • monocarboxylic acids such as, for example, benzoic acid, tert-butylbenzoic acid, hexahydro benzoic acid and saturated aliphatic monocarboxylic acids can also be added during the polyester preparation.
  • polyols such as
  • Suitable compounds for reacting with polycarboxylic acids include monoepoxides such as, for example, ethylene oxide, propylene oxide, monocarboxylic acid glycidyl ester (for example Cardura E10TM; Shell) or phenyl glycidyl ether.
  • monoepoxides such as, for example, ethylene oxide, propylene oxide, monocarboxylic acid glycidyl ester (for example Cardura E10TM; Shell) or phenyl glycidyl ether.
  • polyesters are prepared, using methods known per se, by esterification or transesterification, optionally in the presence of customary catalysts such as, for example, dibutyl tin oxide or tetrabutyl titanate, a suitable choice of the preparation conditions and of the COOH/OH ratio yielding end products with an acid number between 15 and 150.
  • customary catalysts such as, for example, dibutyl tin oxide or tetrabutyl titanate
  • the preparation and testing of the powder coating can take place in a customary manner, for example as described in Misev, Powder Coatings; Chemistry and Technology (Wiley and Sons, 1991) pp. 225-226.
  • the powder coating can also contain mixtures of polyesters and polyacrylates.
  • other resins such as, for example, an epoxy resin, can also be included in the powder coating composition.
  • Suitable pigments include, for example, inorganic pigments such as titanium dioxide, zinc sulphide, iron oxide and chromium oxide, and organic pigments such as azo compounds.
  • Suitable fillers include, for example, metal oxides, silicates, carbonates and sulphates.
  • compositions according to the invention can be used as coating agents for metal, wood and plastic substrates.
  • Examples are general-purpose industrial top coats, top coats on machinery and equipment, in particular top coats on metal, for example for tins, domestic and other small equipment, cars and the like.
  • the invention will be elucidated with the following, non-restrictive examples and comparative example.
  • Example I was repeated, use being made of the listed ingredients in the following amounts by weight (Table I).
  • Example 1 The procedure of Example 1 was repeated, to make powder coatings from the ingredients listed in the following table A in the indicated amounts by weight. No acetyl diethanol amine was added.
  • Benzoin 2.5 The powder coatings according to Examples I, II and Comparative Example A were electrostatically applied to steel panels and cured, during 15 minutes, at 180°C.
  • the blister limit was determined via electromagnetic induction (see the already cited Misev, Powder Coatings, pp. 295-296).
  • the powder coating compositions according to the present invention having the specified combinations of ⁇ - hydroxyalkylamides at a constant amount of benzoin yielded coatings having a desirable higher blister limit.
  • the coatings obtained using the powder coating compositions according to the present invention also retained the desired mechanical properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention se rapporte à une composition de revêtement en poudre, qui comprend comme liant un polymère contenant des groupes d'acide carboxylique libres et comme agent de réticulation un composé contenant des groupes β-hydroxyalkylamide. L'agent de réticulation est constitué par une combinaison d'au moins deux composés contenant des groupes β-hydroxyalkylamide. Chacun de ces composés comporte des fonctions β-hydroxyalkylamide différentes, le premier composé ayant un nombre de fonctions β-hydroxyalkylamide supérieur ou égal à 3 et le second composé ayant un nombre de fonctions β-hydroxyalkylamide inférieur ou égal à 3.
EP93918083A 1992-07-29 1993-07-21 Composition de revetement en poudre avec agent de reticulation a base d'hydroxyalkylamide Withdrawn EP0652911A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
BE9200687 1992-07-29
BE9200687A BE1006097A3 (nl) 1992-07-29 1992-07-29 Poederverf op basis van een polymeer met vrije carbonzuurgroepen als bindmiddel en een beta-hydroxyalkylamidegroepen bevattende verbinding als crosslinker.
PCT/NL1993/000155 WO1994003545A1 (fr) 1992-07-29 1993-07-21 Composition de revetement en poudre avec agent de reticulation a base d'hydroxyalkylamide

Publications (1)

Publication Number Publication Date
EP0652911A1 true EP0652911A1 (fr) 1995-05-17

Family

ID=3886379

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93918083A Withdrawn EP0652911A1 (fr) 1992-07-29 1993-07-21 Composition de revetement en poudre avec agent de reticulation a base d'hydroxyalkylamide

Country Status (6)

Country Link
EP (1) EP0652911A1 (fr)
CN (1) CN1086836A (fr)
AU (1) AU664482B2 (fr)
BE (1) BE1006097A3 (fr)
TW (1) TW248568B (fr)
WO (1) WO1994003545A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000055266A1 (fr) * 1999-03-12 2000-09-21 Sir Industriale S.P.A. MELANGES D'AMIDES β-HYDROXYALKYLE ET LEUR UTILISATION COMME AGENTS DE RETICULATION DANS LA PREPARATION DE PEINTURES EN POUDRE

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5401790A (en) * 1994-03-31 1995-03-28 Ppg Industries, Inc. Waterborne coating compositions having improved smoothness
DE4430400A1 (de) * 1994-08-26 1996-02-29 Inventa Ag Wärmehärtbares Beschichtungssystem aus mehreren Bindemittelharzen
TW385328B (en) * 1995-06-14 2000-03-21 Ciba Sc Holding Ag Corrosion inhibitors in powder coatings
US5744531A (en) * 1996-06-24 1998-04-28 Ppg Industries, Inc. Anionic electrocoating compositions containing hydroxyalkylamide curing agents
DK0839884T3 (da) * 1996-10-30 2000-08-28 Inventa Ag Termohærdende coatingmasser
US5858549A (en) * 1997-01-07 1999-01-12 National Starch And Chemical Investment Holding Corporation (Hydroxyalkyl)urea crosslinking agents
US5840822A (en) * 1997-09-02 1998-11-24 National Starch And Chemical Investment Holding Corporation Mono(hydroxyalkyl)urea and oxazolidone crosslinking agents
NL1007186C2 (nl) * 1997-10-01 1999-04-07 Dsm Nv ß-hydroxyalkylamide groepen bevattend condensatiepolymeer.
DE10004136C2 (de) * 2000-01-31 2001-11-29 Ems Chemie Ag Wärmehärtbare Beschichtungsmassen
AU2002352080A1 (en) * 2001-12-06 2003-06-17 Vantico Ag Heat-curable resin composition
CA2600717C (fr) * 2005-03-18 2013-08-27 Battelle Memorial Institute Resines, formulations a basse temperature, et revetements en decoulant
EP1743924A1 (fr) 2005-07-11 2007-01-17 DSM IP Assets B.V. Composition de peinture en poudre
WO2009090234A1 (fr) * 2008-01-17 2009-07-23 Dsm Ip Assets B.V. Composition de revêtement pulvérulent thermodurcissable

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4801680A (en) * 1987-12-30 1989-01-31 Ppg Industries, Inc. Hydroxyalkylamide powder coating curing system
US5101073A (en) * 1990-08-27 1992-03-31 Rohm And Haas Company Production of β-hydroxyalkylamides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9403545A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000055266A1 (fr) * 1999-03-12 2000-09-21 Sir Industriale S.P.A. MELANGES D'AMIDES β-HYDROXYALKYLE ET LEUR UTILISATION COMME AGENTS DE RETICULATION DANS LA PREPARATION DE PEINTURES EN POUDRE

Also Published As

Publication number Publication date
CN1086836A (zh) 1994-05-18
TW248568B (fr) 1995-06-01
BE1006097A3 (nl) 1994-05-10
AU664482B2 (en) 1995-11-16
AU4763193A (en) 1994-03-03
WO1994003545A1 (fr) 1994-02-17

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