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WO2003004574A1 - Compositions en poudre thermodurcissables pour revetements - Google Patents

Compositions en poudre thermodurcissables pour revetements Download PDF

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Publication number
WO2003004574A1
WO2003004574A1 PCT/EP2002/007063 EP0207063W WO03004574A1 WO 2003004574 A1 WO2003004574 A1 WO 2003004574A1 EP 0207063 W EP0207063 W EP 0207063W WO 03004574 A1 WO03004574 A1 WO 03004574A1
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WO
WIPO (PCT)
Prior art keywords
mole
acid
neopentyl glycol
polyacid
thermosetting compositions
Prior art date
Application number
PCT/EP2002/007063
Other languages
English (en)
Inventor
Luc Moens
Nele Knoops
Daniel Maetens
Original Assignee
Ucb, S.A.
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 Ucb, S.A. filed Critical Ucb, S.A.
Publication of WO2003004574A1 publication Critical patent/WO2003004574A1/fr

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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

Definitions

  • thermosetting powder compositions comprising a mixture of an isophthalic acid and neopentyl glycol hydroxypivalate rich carboxyl functionalised polyester along with an epoxy group containing cross-linking agent.
  • the invention also relates to the use of said compositions for the preparation of powdered paints and varnishes for the making of coatings and to coatings obtained therewith.
  • Thermosetting powder compositions are well known in the art and are widely used as paints and varnishes for coating the most various articles.
  • the advantages of these powder coatings are numerous; on the one hand, the problems associated with solvents are completely eliminated, and on the other hand, the powders are used without any loss since only the powder in direct contact with the substrate is retained on the article, the excess powder being, in principle, entirely recoverable and reusable.
  • the powder coating compositions are preferred to coating compositions in the form of solutions in organic solvents.
  • thermosetting powder compositions have already been widely used in the coating of domestic electrical appliances, automobile industry accessories, and the like. They generally contain a thermosetting organic binder, fillers, pigments, catalysts and various additives used to adapt their properties to their intended use.
  • thermosetting powder compositions There are various types of thermosetting powder compositions.
  • the best known compositions contain either a mixture of carboxyl group-containing polymers, such as a carboxyl group-containing polyester or polyacrylate, and epoxy compounds, such as triglycidyl isocyanurate, glycidyl group-containing acrylic copolymers or ⁇ - hydroxyalkylamides or a mixture of hydroxyl group-containing polymers, most often a hydroxyl group-containing polyester, with blocked or non-blocked isocyanates, rnelarnine resins, and the like.
  • carboxyl group-containing polymers such as a carboxyl group-containing polyester or polyacrylate
  • epoxy compounds such as triglycidyl isocyanurate, glycidyl group-containing acrylic copolymers or ⁇ - hydroxyalkylamides or a mixture of hydroxyl group-containing polymers, most often a hydroxyl group-containing polyester, with blocked or non-blocked is
  • polyesters are usually prepared from aromatic dicarboxylic acids, mainly terephthalic acid and isophthalic acid and optionally a minor proportion of aliphatic or cycloaliphatic dicarboxylic acids, and from various polyols such as ethylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, and the like.
  • polyesters based on aromatic dicarboxylic acids when they are used with an appropriate cross-linking agent, provide thermosetting compositions giving paint and varnish coatings possessing good properties, both as regards their appearance and as regards their mechanical properties such as impact resistance, flexibility, etc.
  • polyesters and the powders derived from them often are used because of their remarkable weatherability- characteristics.
  • These polyesters mostly are derived from isophthalic acid, being the most important acid constituent among others and are commonly used with triglycidyl isocyanurate (TGIC) as the cross-linking agent.
  • TGIC triglycidyl isocyanurate
  • Powder paints comprising an isophthalic rich polyester resin and an epoxy compound as hardener giving coatings having an unique combination of properties, such as an improved weatherability along with impact resistance, already have been subject to a certain number of publications.
  • US 5.321.100 discloses powder paints comprising a polyepoxy compound and an acid functional polyester having an acid number of from 15 through 70 mg KOH/g which is substantially based on dicarboxylic acid units containing at least 15% mole of isophthalic acid, preferably at least 75% mole, and at least 5% mole of 1,4- cyclohexanedicarboxylic acid.
  • the alcohol constituents of the polyester comprises at least 50% mole of branched aliphatic glycols having 5 to 11 carbon atoms.
  • 1,4-cyclohexanedicarboxylic acid has an unexpected influence on the impact resistance of the coatings derived from polyesters with a preponderant amount of isophthalic acid.
  • thermosetting powder coating compositions derived from carboxyl functional isophthalic acid rich amorphous polyesters is the use of semi-crystalline acid functional polyesters as co-reactable part of the carboxylic acid amorphous resin in a binder along with a polyepoxy compound or a ⁇ - hydroxyalkylamides, such as claimed in e.g. WO 91/14745 or WO 97/20895.
  • US 5.418.309 provides a powder coating composition having good weather resistance, hardness and processability.
  • the powder composition comprises an hydroxyl functional polyester (hydroxyl number from 10 to 100 mg KOH/g) or a carboxyl functional polyester (acid number of 10 to 100 mg KOH/g) and a curing agent selected from an epoxy compound or a blocked isocyanate compound.
  • the polyester is made of at least 80% mole of an aromatic dicarboxylic acid, preferably isophthalic or terephthalic acid, and of a polyol constituent comprising at least 50% mole of neopentylglycol and 1 to 10% by weight of a linear chain diol having fom 8 to 16 carbon atoms or 2-methyl-l,8-octanediol and mixtures thereof. Additionally, other polyols can be used. According to this invention, the combination of an aromatic acid and of the C8-C16 diol of the polyester affords the good properties of the coatings obtained from the powder compositions containing it.
  • the powder coating compositions comprising the binder of the present invention, based on a carboxylic acid group containing amorphous isophthalic acid and neopentyl glycol hydroxypivalate rich polyester, in combination with an epoxy group containing cross- linking agent, give paint films proving very smooth coatings, exhibiting excellent outdoor durability and flexibility, without any defects.
  • thermosetting compositions for coatings characterised in that they comprise: a) 70-98 % by weight of an amorphous carboxylic acid group containing polyester composed of polycarboxylic units containing from 80 to 100 % mole of isophthalic acid and from 0 to 20% mole of another linear or branched aliphatic polyacid, or aromatic polyacid, and of a polyol constituent comprising from 10 to 60% mole of neopentyl glycol hydroxypivalate, from 40 to 90% mole of neopentyl glycol and from 0 to 30% mole and preferably from 0 to 20% mole of another aliphatic and/or cycloaliphatic polyol, excluding linear chain diols having 8 to 16 carbon atoms and 2-methyl-l,8- octanediol; b) 2-30% by weight of an epoxy group containing cross-linking agent.
  • compositions of the present invention do not contain a semi-crystalline polyester containing carboxyl groups.
  • neopentyl glycol hydroxypivalate and neopentyl glycol instead of neopentyl glycol hydroxypivalate and neopentyl glycol, use can be made of an amount of hydroxypivalic acid corresponding to the needed amount of neopentyl glycol hydroxypivalate.
  • hydroxypivalic acid is first allowed to react with the corresponding amount of neopentyl glycol before the other polyols are put into reaction.
  • the carboxyl functional amorphous polyester of the present invention further is characterised by: an acid number from 15 to 70 mg KOH/g, preferably from 20 to 50 mg KOH/g and more preferably from 25 to 35 mg KOH/g a number averaged molecular weight ranging from 1600 to 8600, preferably from 2200 to 7000 and more preferably from 3200 to 6500 as measured by gel permeation chromatography (GPC) a glass transition temperature Tg from 40 to 80°C and preferably from 50 to 70°C as measured by differential scanning calorimetry (DSC) according to ASTM D3418 with a heating gradient of 20°C per minute
  • the acid constituent of the amorphous polyester is from 80 to 100 % mole composed of isophthalic acid and for 0 to 20% mole of another polyacid constituent selected from one or more linear or branched aliphatic or aromatic polyacids, such as: fumaric acid, maleic acid, phthalic anhydride, terephthalic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azealic acid, sebacic acid, 1, 12-dodecanedioic acid, trimellitic acid or pyromellitic acid, etc., or the corresponding anhydrides.
  • another polyacid constituent selected from one or more linear or branched aliphatic or aromatic polyacids, such as: fumaric acid, maleic acid, phthalic anhydride, terephthalic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azealic acid, sebacic acid,
  • the glycol constituent of the amorphous polyester is for 10 to 60% mole composed of neopentyl glycol hydroxypivalate, for 40 to 90% mole composed of neopentyl glycol, and preferably 40 to 80% mole, and for 0 to 30% mole and preferably for 0 to 20% mole of another polyol constituent selected from one or more aliphatic or cycloaliphatic polyols, other than linear chain diols having 8 to 16 carbon atoms and 2-methyl-l,8-octanediol..
  • polystyrene resin selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-methyl-l,3-propanediol, hydrogenated Bisphenol A, 2- butyl-2-ethyl-l,3-propanediol, trimethylolpropane, ditrimethylolpropane, pentaerythrytol, etc.
  • the polyester according to the present invention is composed of polycarboxylic acid units containing from 80 to 100 % mole of isophthalic acid, from 0 to 20% mole of terephthalic acid and from 0 to 15% mole of trimellitic anhydride or pyromellitic anhydride, and of polyol constituents containing from 10 to 60% mole of neopentyl glycol hydroxypivalate, from 40 to 90% mole of neopentyl glycol and from 0 to 20% mole of trimethylolpropane or pentaerythrytol.
  • the carboxylic acid group containing amorphous polyester is prepared using conventional esterification techniques well known in the art.
  • the polyester is prepared according to a procedure consisting of one or more reaction steps.
  • polyesters For the preparation of these polyesters, a conventional reactor equipped with a stirrer, an inert gas (nitrogen) inlet, a thermocouple, a distillation column connected to a water-cooled condenser, a water separator and a vacuum connection tube is used.
  • the esterification conditions used to prepare the polyesters are conventional, namely a standard esterification catalyst, such as dibutyltin oxide, dibutyltin dilaurate, n- butyltin trioctoate, sulphuric acid or a sulphonic acid, can be used in an amount from 0.05 to 1.50% by weight of the reactants and optionally, colour stabilisers, for example, phenolic antioxidants such as Irganox 1010 (Ciba) or phosphonite- and phosphite-type stabilisers such as tributylphosphite, can be added in an amount from 0 to 1% by weight of the reactants.
  • a standard esterification catalyst such as dibutyltin oxide, dibutyltin dilaurate, n- butyltin trioctoate, sulphuric acid or a sulphonic acid
  • colour stabilisers for example, phenolic antioxidants such as Irganox 1010
  • Polyesterification is generally carried out at a temperature which is gradually increased from 130°C to about 190 to 250°C, first under normal pressure, then, when necessary, under reduced pressure at the end of each process step, while maintaining these operating conditions until a polyester is obtained, which has the desired hydroxyl and/or acid number.
  • the degree of esterification is followed by determining the amount of water formed in the course of the reaction and the properties of the obtained polyester, for example the hydroxyl number, the acid number, the molecular weight or the viscosity.
  • crosslinking catalysts can optionally be added to the polyester while it is still in the molten state. These catalysts are added in order to accelerate crosslinking of the thermosetting powder compositions during curing.
  • catalysts examples include amines, such as 2-phenylimidazoline, phosphines, such as triphenylphosphine, ammonium salts, such as tetrabutylammonium bromide or tetrapropylammonium chloride, phosphonium salts, such as ethyltriphenylphosphonium bromide or tetraphenylphosphonium chloride. These catalysts are preferably used in an amount of 0 to 5% with respect of the weight of the polyester.
  • the carboxyl group containing amorphous polyester, as described above, is part of a binder system along with an epoxy group containing cross-linking agent, in the preparation of powder coating compositions for use as paint or clear lacquer.
  • Suitable cross-linking agents are polyepoxy compounds solid at room temperature and containing at least two epoxy groups per molecule such as, for example, triglycidylisocyanurate like the one marketed under the name Araldite PT810 (Vantico) or the diglycidylterephthalate/triglycidyltrimellitate 75/25 mixture Araldite PT910 (Vantico).
  • Use can also be made of acrylic copolymers containing glycidyl groups obtained from glycidyl methacrylate, glycidyl acrylate, 1,2-ethyleneglycol glycidylether(meth)acrylate, 1 ,3-propyleneglycolglycidylether(meth)acrylate, 1,4- butyleneglycolglycidylether(meth)acrylate.
  • the epoxy group containing cross-linking agent described herein above is used in an amount from 0.25 to 1.40 preferably from 0.60 to 1.05 equivalent of carboxyl group present in the amorphous polyester per equivalent of epoxy groups.
  • compositions within the scope of the present invention can also include flow control agents such as Resiflow PV5 (Worlee), Modaflow (Monsanto), Acronal 4F (BASF), etc., and degassing agents such as benzoin (BASF) etc.
  • flow control agents such as Resiflow PV5 (Worlee), Modaflow (Monsanto), Acronal 4F (BASF), etc.
  • degassing agents such as benzoin (BASF) etc.
  • UV-light absorbers such as Tinuvin 900 (Ciba), hindered amine light stabilisers represented by Tinuvin 144 (Ciba), other stabilising agents such as Tinuvin 312 and 1130 (Ciba), antioxidants such as Irganox 1010 (Ciba) and stabilisers from the phosphonite or phosphite type can be added.
  • Both, pigmented systems as well as clear lacquers can be prepared.
  • a variety of dyes and pigments can be utilised in the composition of this invention.
  • useful pigments and dyes are: metallic oxides such as titaniumdioxide, ironoxide, zincoxide and the like, metal hydroxides, metal powders, sulphides, sulphates, carbonates, silicates such as ammoniumsilicate, carbon black, talc, china clay, barytes, iron blues, leadblues, organic reds, organic maroons and the like.
  • the components of the composition according to the invention may be mixed by dry blending in a mixer or blender (e.g. drum mixer).
  • the prernix is then homogenised at temperatures ranging from 70 to 150°C in a single screw extruder such as the BUSS- Ko-Kneter or a double screw extruder such as the PRISM or APV.
  • the extrudate when cooled down, is grounded to a powder with a particle size ranging from 10 to 150 um.
  • the powdered composition may be deposited on the substrate by use of a powder gun such as an electrostatic CORONA gun or TRIBO gun.
  • well known methods of powder deposition such as the fluidised bed technique can be used. After deposition the powder is heated to a temperature between 140 and 250°C, causing the particles to flow and fuse together to form a smooth, uniform, continuous, uncratered coating on the substrate surface.
  • a mixture of 232.8 parts of neopentyl glycol, 232.8 parts of neopentyl glycol hydroxypivalate and 16.7 parts of trimethylolpropane is placed in a conventional four neck round bottom flask equipped with a stirrer, a distillation column connected to a water cooled condenser, an inlet for nitrogen and a thermometer attached to a thermoregulator.
  • the flask contents are heated, while stirring under nitrogen, to a temperature of circa 130°C at which point 643.6 parts of isophthalic acid and 2.5 parts of n- butyltintrioctoate are added.
  • the heating is continued gradually to a temperature of 230°C.
  • Water is distilled from the reactor from 180°C on. When distillation under atmospheric pressure stops, a vacuum of 50 mm Hg is gradually applied. After three hours at 230°C and 50 mm Hg, following characteristics are obtained:
  • Example 2 A mixture of 270.9 parts of neopentyl glycol, 180.6 parts of neopentyl glycol hydroxypivalate and 16.7 parts of trimethylolpropane is placed in a reactor as for Example 1. At a temperature of 130°C, 130.6 parts of terephthalic acid, 413.5 parts of isophthalic acid and 2.5 parts of n-butyltintrioctoate are added. The reaction is continued at 220°C under atmospheric pressure until about 95% of the theoretical amount of water is distilled and a transparent hydroxyl functionalised prepolymer with following characteristics is obtained:
  • Example 1 Adopting the procedure of Example 1 as series of examples, accordingly the present invention, (Ex. 3 - Ex. 5) as well as a series of comparative examples (Comp. Ex. 1 - Comp. Ex. 3) were prepared.
  • the monomer composition as well as the resin characteristics are given in table 1.
  • Example 6 The polyesters as illustrated above, are then formulated to a powder accordingly to one of the formulations as mentioned below.
  • the powders are prepared first by dry blending of the different components and then by homogenisation in the melt using a PRISM 16 mm L/D 15/1 twin screw extruder at an extrusion temperature of 85°C.
  • the homogenised mix is then cooled and grinded in an Alpine. Subsequently the powder is sieved to obtain a particle size between 10 and 110 um.
  • the powder thus obtained is deposited on chromated (Cr6+) aluminium H5005, DIN 50939 with a thickness of 1 mm, by electrostatic deposition using the GEMA - Volstatic PCG 1 spraygun. At a film thickness of about 80 ⁇ m the panels are transferred to an air-ventilated oven, where curing proceeds for 15 minutes at a temperature of 200°C.
  • the paint characteristics for the finished coatings obtained from the polyesters of the present invention (Ex. 1 to Ex. 5) as well as from the polyesters as illustrated by way of comparison (Comp. Ex. 1 to Comp. Ex. 3) are given in table 2.
  • PT910 diglycidylterephthalate/triglycidyltrimellitate 75/25 blend
  • Column 5 indicates the 60° gloss, measured according to ASTM D523
  • Column 6 indicates the direct impact strength according to ASTM D2794. The highest impact which does not crack the coating is recorded in kg.cm.
  • Column 7 indicates the reverse impact strength according to ASTM D2794. The highest impact which does not crack the coating is recorded in kg.cm.
  • neopentyl glycol hydroxypivalate clearly appear from comparing example 13 to example 17. Yet as proven by example 16, based on comparative example 2, neopentyl glycol hydroxypivalate quantities of less than 10% mole do not induce flexibility. Besides an outstanding flexibility and flow, the powder coating compositions of the present invention prove to satisfy an excellent outdoor resistance comparable to the currently used nowadays commercial polyester based powders.
  • powder compositions according to the present invention containing as a binder a combination of the carboxyl functional polyester according to the present invention along with an epoxy cross-linking agent prove upon application and curing an unique combination of properties such as a good flexibility, outstanding flow and gloss and a remarkable weatherability.

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

Abstract

Cette invention porte sur des compositions thermodurcissables en poudre pour revêtements, comprenant un groupe acide carboxylique contenant un polyester composé d'un constituant polyacide renfermant entre 80 et 100 % en mole d'acide isophtalique et entre 0 et 20 % en mole d'un autre polyacide aliphatique linéaire ou ramifié ou d'un polyacide aromatique et d'un constituant polyol comprenant entre 10 et 60 % en mole d'hydroxypivalate néopentylglycol, entre 40 et 90 % en mole de néopentylglycol et entre 0 et 30 % en mole et de préférence entre 0 et 20 % en mole d'un autre polyol aliphatique et/ou cycloaliphatique. L'agent de réticulation pour le polyester est un composé contenant un groupe époxy. Les revêtements obtenus avec ces poudres sont très doux et ne comportent pas de trous d'épingle ou autre défauts et présentent d'excellentes propriétés de durabilité et de flexibilité en extérieur.
PCT/EP2002/007063 2001-07-02 2002-06-26 Compositions en poudre thermodurcissables pour revetements WO2003004574A1 (fr)

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EP01116092.6 2001-07-02
EP01116092 2001-07-02

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WO2003004574A1 true WO2003004574A1 (fr) 2003-01-16

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010094811A1 (fr) 2009-03-27 2010-08-26 Dsm Ip Assets B.V. Composition de revêtement en poudre comprenant un polyester et un bêta-hydroxyalkylamide servant d'agent de réticulation
CN104277207A (zh) * 2014-10-31 2015-01-14 安徽神剑新材料股份有限公司 一种超耐候低温固化型聚酯树脂
CN104292443A (zh) * 2014-10-31 2015-01-21 安徽神剑新材料股份有限公司 一种超耐候低温固化型聚酯树脂的制备方法
CN114196000A (zh) * 2021-12-23 2022-03-18 安徽神剑新材料股份有限公司 一种高涂层Tg抗划伤不含TMA的聚酯树脂及其制备方法、一种粉末涂料

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6090268A (ja) * 1983-10-21 1985-05-21 Toyobo Co Ltd 塗装鋼板用塗料組成物
US5321100A (en) * 1989-03-23 1994-06-14 Dsm N.V. Powder paint and a polyester resin for powder paint
WO1997020895A1 (fr) * 1995-12-06 1997-06-12 Ucb, S.A. Compositions thermodurcissables en poudre pour revetements

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6090268A (ja) * 1983-10-21 1985-05-21 Toyobo Co Ltd 塗装鋼板用塗料組成物
US5321100A (en) * 1989-03-23 1994-06-14 Dsm N.V. Powder paint and a polyester resin for powder paint
WO1997020895A1 (fr) * 1995-12-06 1997-06-12 Ucb, S.A. Compositions thermodurcissables en poudre pour revetements

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 009, no. 233 (C - 304) 19 September 1985 (1985-09-19) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010094811A1 (fr) 2009-03-27 2010-08-26 Dsm Ip Assets B.V. Composition de revêtement en poudre comprenant un polyester et un bêta-hydroxyalkylamide servant d'agent de réticulation
CN104277207A (zh) * 2014-10-31 2015-01-14 安徽神剑新材料股份有限公司 一种超耐候低温固化型聚酯树脂
CN104292443A (zh) * 2014-10-31 2015-01-21 安徽神剑新材料股份有限公司 一种超耐候低温固化型聚酯树脂的制备方法
CN114196000A (zh) * 2021-12-23 2022-03-18 安徽神剑新材料股份有限公司 一种高涂层Tg抗划伤不含TMA的聚酯树脂及其制备方法、一种粉末涂料

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