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WO1996036674A1 - Revetements en continu de bandes en couches larges et composition et procede pour preparer de tels revetements - Google Patents

Revetements en continu de bandes en couches larges et composition et procede pour preparer de tels revetements Download PDF

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Publication number
WO1996036674A1
WO1996036674A1 PCT/NL1996/000196 NL9600196W WO9636674A1 WO 1996036674 A1 WO1996036674 A1 WO 1996036674A1 NL 9600196 W NL9600196 W NL 9600196W WO 9636674 A1 WO9636674 A1 WO 9636674A1
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WO
WIPO (PCT)
Prior art keywords
resin
acid
koh
gram
composition
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.)
Ceased
Application number
PCT/NL1996/000196
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English (en)
Inventor
Albert Heyenk
Johannes Wilhelmus Besamusca
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
Priority to AU57038/96A priority Critical patent/AU5703896A/en
Publication of WO1996036674A1 publication Critical patent/WO1996036674A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the present invention relates to thick-layer coil coatings.
  • polyester based composition that includes crosslinking agents that contain isocyanate groups, which can provide a coating film having a maximum (dry) coat thickness of 35 ⁇ m.
  • elimination products such as methanol, butanol and blocking agent, are released, which may cause surface defects in the cured film.
  • the coating thickness is determined via ISO
  • composition that, when suitably cured, provides a coil coating possessing the aforementioned properties.
  • a composition which comprises an acid-functional polyester having an acid number in the range of about 10 to about 90 mg of KOH/gram of resin, a hydroxyl number lower than 5 mg of KOH/gram of resin and a molecular weight (Mn) in the range of about 1500 to 10,000, a crosslinking agent containing epoxy groups, and an organic solvent.
  • coil coatings having a primer and/or top coat layer thickness between 5 ⁇ m and 60 ⁇ m can be obtained. This range can indicate the thickness of each individual layer.
  • the coatings obtained also exhibit high quality in terms of scratch resistance, hardness, flexibility and anti-corrosion properties.
  • the glass transition temperature of the resulting cured coil coating is generally at least 40°C. Consequently the desired hardness, scratch resistance, chemical resistance, and corrosion resistance of the coating are ensured.
  • the hydroxyl number of the acid- functional polyester is about 0 mg of KOH/gram resin.
  • the acid number is in the range of about 30 to about 70 mg of KOH/gram resin.
  • the molecular weight (Mn) is in the range of about 2000 to 7000.
  • Suitable compounds containing epoxy-groups for use as the crosslinker are, for instance, bisphenol-A epoxy resins (for instance Epikote 828TM, Epikote 1001TM and Epikote 1004TM from Shell), hydrogenated bisphenol-A epoxy compounds, aliphatic epoxy compounds, epoxidized alkyd resins, epoxidized oils (for instance epoxidized linseed oil or soya bean oil), epoxidized borates and triglycidyl isocyanurate.
  • a bisphenol-A epoxy resin is selected as the crosslinking agent.
  • a suitable crosslinking agent can include a mixture of a compound containing epoxy- groups with another compound that contains melamine groups or isocyanate groups.
  • the mixture of crosslinking agents preferably contains more than about 90 wt.% of the crosslinking agent containing epoxy- groups.
  • the binder composition according to the invention has an equivalent ratio carboxyl : epoxy equivalent ratio in the range of about 0.85 : 1 to 1 : 0.85 and more preferably in the range of about 0.9 : 1 to 1 : 0.9.
  • the acid functional polyester resin can also contain a melt-incorporated solid catalyst. It is also possible to use a liquid catalyst or to mix in a catalyst solution in the paint formulation.
  • Suitable catalysts are described by Madac et al., in Kinetics and Mechanisms of Polyesterifications, Advances in Polymer Science, 182-198 (1985) which is incorporated herein by reference.
  • suitable classes of catalysts selectable for the present invention include, N-dialkylamine pyridines, tertiary - A -
  • exemplary catalysts include by way of example 2,4,6-tri(dimethylaminomethyl)phenol, dimethylbenzylamine, N-dimethylamino pyridine, benzotriazole, triethyl amine, triphenyl amine, 4,5- diphenyl imidazole, 1-ethyl imidazole, 2-methyl imidazole, 4-methyl imidazole, ethyl imidazole carboxylate, 5,6-dimethyl benzimidazole, 1-benzyl imidazole, imidazole, 1,1-carbonyl diimidazole, benzyl trimethyl ammonium chloride, choline chloride, triphenyl ethyl phosphonium bromide, tetramethyl guanidine (TMG) , isocyanate-TMG
  • a metal salt of a carboxylic acid or an alcohol or a metal hydroxide can also be used as the catalyst.
  • Suitable salts include, for example, sodium stearate, lithium stearate, lithium acetate, sodium benzoate, sodium neodecanoate, lithium benzoate, sodium laurate, lithium laurate, lithium adipate, sodium octanoate, lithium octanoate, lithium neodecanoate and lithium versatate.
  • the weight percentage of the catalysts relative to the polyester generally is in the range of about 0.1 wt.% to about 5 wt.%.
  • the carboxyl-functional polyester preferably is prepared by reaction between a hydroxyl-functional polyester and an acid anhydride or a dicarboxylic acid.
  • Suitable acid anhydrides include, for example, phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, or a combination thereof.
  • trimellitic anhydride and hexahydrophthalic anhydride are used.
  • Suitable dicarboxylic acids include, for example, adipic acid, isophthalic acid, hexahydroterephthalic acid, and sebacic acid.
  • the reaction between the hydroxyl-functional polyester and the acid anhydride or the dicarboxylic acid preferably takes place (in a second step) after synthesis of the hydroxyl-functional polyester is complete.
  • the molar ratio between the hydroxyl groups and the acid anhydride or dicarboxylic acid groups preferably is about equimolar. In this way, a polyester with a hydroxyl number lower than about 5, and more preferably about 0, can be obtained.
  • the carboxyl-functional polyester can also be obtained directly by means of reaction of polyalcohols with acids or acid anhydrides.
  • the molar ratio between the polyalcohols and the acids or acid anhydrides is preferably in the range of about 1.0:1.2 to about 1.0:1.0 so as to obtain a polyester having a hydroxyl number lower than about 5, and more preferably about 0.
  • Suitable polyalcohols for the preparation of the carboxyl-functional polyester include, by way of example, ethylene glycol, propylene glycol, diethylene glycol, butane diol (1,4), hexane diol (1,6), neopentyl glycol, 2-methyl-l,3-propane diol, 1,3-butane diol, 1,3-propane diol, 1,2-propane diol, 2-ethyl-2-butyl- 1,3-propane diol, trimethylpentane diol, hydroxypivalineopentylglycol ester, tricyclodecane dimethanol, cyclohexane dimethanol, biphenol-A- bishydroxyethyl ether, trimethylol propane, pentaerythritol, or a combination thereof.
  • Suitable acids for the preparation of the carboxyl-functional polyesters include, by way of example, isophthalic acid, terephthalic acid (dimethyl ester), adipic acid, sebacic acid, hexahydroterephthalic acid (CHDA), decane dicarboxylic acid, 5-6-butylisophthalic acid, dimerized fatty acids, or a combination thereof.
  • Suitable acid anhydrides include, by way of example, phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, or a combination thereof.
  • the acid is selected from the group consisting of isophthalic acid, terephthalic acid, adipic acid, or a combination thereof.
  • the esterification reaction preferably takes place under a nitrogen atmosphere at temperatures in the range of about 160°C to about 260°C.
  • Catalysts such as, for example, dibutyl tin oxide, phosphorous acid, tin chloride, butylchlorotin dihydroxide (FASCATTM) , or tetrabutoxy titanate, and suitable antioxidants such as, for example, t inonylphenyl phosphite and triphenyl phosphite, can be used as additives.
  • Water released during the esterification reaction preferably is distilled off and the desired esterification degree is obtained by applying an azeotropic distillation and/or a vacuum destination in the final stage.
  • the reaction yields a polyester which can be dissolved in an organic solvent or a mixture of organic solvents.
  • the ratio of polyester to organic solvent is selected, or can be determined through routine experimentation, to provide a desired solids content.
  • the solvent can be added directly after the polyester synthesis, or after synthesis and during the preparation of the composition.
  • the solids content of the polyester preferably is in the range of about 50% to about 100%.
  • Suitable solvents include, by way of example, aromatic hydrocarbon resins (for example, Solvesso types), N-methyl pyrrolidone, xylene, propylene glycolmonomethyl ether, methyl-propylene glycol acetate (PMA) , ethyl ethoxy propionate, ethylene-propylene glycol acetate, isophoron, dibasic ester (DBE) and butyl glycol. These solvents can be used alone or in any combination thereof. By preference, an aromatic hydrocarbon, PMA, DBE or a combination thereof is used.
  • Coil coatings can be obtained by generally known processes, such as described for instance in "Coil Coatings” by Joseph E. Gaske (Federation of
  • the curing conditions and additives can be chosen on the basis of the desired peak metal temperature (PMT), and the nature and the thickness of the substrate.
  • the curing time preferably is between about 20 seconds and about 70 seconds.
  • the curing is preferably conducted at temperatures between about 250°C and about 400°C, which results in a PMT between about 204°C and about 249°C.
  • Suitable substrates include, for example, steel, tinned steel and aluminum.
  • the coatings prepared in accordance with the present invention are suitable as primer and as top coat for coils.
  • the coatings can suitably be applied, by way of example, in part or in whole, to coils employed in household equipment and appliances, such as, for example, ref igerators, freezers, ovens, microwave ovens, and boilers.
  • the coatings of the present invention are suitable as coatings for caravans and as facade coating.
  • the appearance of the coatings can be manipulated by the addition of pigments.
  • the monomers for preparing the polyester and the crosslinking agent of the composition of the present invention, and the curing conditions for curing the composition into a coil coating, are preferably selected with consideration of the particular intended application of the coil coating.
  • additives such as, for example, pigments, fillers, stabilizers, dispersing agents, flow promotion agents and de-foaming agents, can be included in the composition of the present invention.
  • composition according to the invention is also suitable for other applications, especially can coatings.
  • desired layer thickness is in general lower and the curing conditions involved in the preparation of can coatings differ from those in coil coating manufacture.
  • the resin obtained was diluted with a mixture consisting of the solvents dibasic ester (DBETM, Du Pont) and propylene glycol methyl ether acetate (in a weight ratio of 1:1) to obtain a solids content of 60% by weight.
  • DBETM solvents dibasic ester
  • propylene glycol methyl ether acetate in a weight ratio of 1:1
  • the acid number of the solid resin was 35 mg KOH/gram resin and the hydroxyl number was 0 mg KOH/gram.
  • the viscosity measured via a Physica Viscolab LC3 at 23°C, was 14.0 Pa.s (according to ISO 3219).
  • the binding agent composition thus obtained was applied onto hot-dipped galvanized steel (Bonder 1303) with a 150 ⁇ m wire coater . After curing in an oven with a stoving cycle of 44 seconds at 380°C, resulting in a PMT of 232-241°C, the following characteristics were determined: - layer thickness: 40 ⁇ m (determined in accordance with ISO 2360)
  • T-bend T (determined in accordance with ASTM D 4145) solvent resistance (methyl ethyl ketone) : 100 dR - pencil hardness; H (determined in accordance with ASTM D 3363) - condensation water resistance: no blistering after 2000 hours (determined in accordance with DIN 50 017) - salt spray: after 1000 hours, a strip of 1-2 mm has come off along the scratch (determined in accordance with DIN 50 021).
  • the maximum reaction temperature was 235°C.
  • azeotropic distillation with xylene was started and continued until an acid number of 3.8 was reached.
  • the resin obtained was diluted with a mixture consisting of the solvents PMA and DBE (in a weight ratio of 1:1) to obtain a solids content of 60%.
  • the acid number of the resin was 3.8 and the hydroxyl number was 30.
  • the viscosity measured in a Physica Viscolab LC3 at 23°C, was 6.9 Pa.s (according to ISO 3219).
  • the molecular weight (Mn) amounted to 3280 (determined by means of GPC on a polystyrene standard).
  • composition thus obtained was applied onto hot dipped galvanized steel (Bonder 1303) with a 150 ⁇ m wire coater. After curing in an oven with a stoving cycle of 44 seconds at 380°C, resulting in a PMT of 232-241°C, the following characteristics were determined:
  • composition according to the invention provides a coil coating having a desirable layer thickness and a good appearance, whereas the composition according to the comparative experiment results in a coating having a large amount of surface defects due to the layer being too thick for hydroxyl-functional polyester-melamine systems.

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  • 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)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Cette invention se rapporte à l'utilisation d'une composition comprenant un polyester à fonction acide ayant un indice d'acidité compris entre 10 et 90 mg de KOH/gramme de résine, un indice hydroxyle inférieur à 5 mg de KOH/gramme de résine et un poids moléculaire (Mn) compris entre 1 500 et 10 000, un agent de réticulation contenant des groupes époxy et un solvant organique, pour obtenir une bande enduite en continu ayant un revêtement avec une couche sèche d'une épaisseur comprise entre 5 νm et 60 νm.
PCT/NL1996/000196 1995-05-18 1996-05-08 Revetements en continu de bandes en couches larges et composition et procede pour preparer de tels revetements Ceased WO1996036674A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57038/96A AU5703896A (en) 1995-05-18 1996-05-08 Thick-layer coil coatings and composition and process for pr eparing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1000387 1995-05-18
NL1000387A NL1000387C2 (nl) 1995-05-18 1995-05-18 Dikke laag coil coatings.

Publications (1)

Publication Number Publication Date
WO1996036674A1 true WO1996036674A1 (fr) 1996-11-21

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ID=19761041

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1996/000196 Ceased WO1996036674A1 (fr) 1995-05-18 1996-05-08 Revetements en continu de bandes en couches larges et composition et procede pour preparer de tels revetements

Country Status (3)

Country Link
AU (1) AU5703896A (fr)
NL (1) NL1000387C2 (fr)
WO (1) WO1996036674A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1007205C2 (nl) * 1997-10-03 1999-04-08 Dsm Nv Coil coating.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3397254A (en) * 1964-09-21 1968-08-13 Union Carbide Corp Carboxy terminated polyesters prepared from tribasic acid anhydrides and hydroxy terminated polyesters
US3650997A (en) * 1970-08-13 1972-03-21 Immont Corp Coating compositions containing epoxy resins and carboxyl terminated polyesters
WO1995006689A1 (fr) * 1993-09-02 1995-03-09 The Dow Chemical Company Composition solide pour revêtement pulverent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3397254A (en) * 1964-09-21 1968-08-13 Union Carbide Corp Carboxy terminated polyesters prepared from tribasic acid anhydrides and hydroxy terminated polyesters
US3650997A (en) * 1970-08-13 1972-03-21 Immont Corp Coating compositions containing epoxy resins and carboxyl terminated polyesters
WO1995006689A1 (fr) * 1993-09-02 1995-03-09 The Dow Chemical Company Composition solide pour revêtement pulverent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1007205C2 (nl) * 1997-10-03 1999-04-08 Dsm Nv Coil coating.

Also Published As

Publication number Publication date
AU5703896A (en) 1996-11-29
NL1000387C2 (nl) 1997-01-21
NL1000387A1 (nl) 1996-11-19

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