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WO2004026981A1 - Composition de liant comprenant un polyester a fonction carboxyle et un $g(b)-hydroxy alkylamide - Google Patents

Composition de liant comprenant un polyester a fonction carboxyle et un $g(b)-hydroxy alkylamide Download PDF

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Publication number
WO2004026981A1
WO2004026981A1 PCT/NL2003/000643 NL0300643W WO2004026981A1 WO 2004026981 A1 WO2004026981 A1 WO 2004026981A1 NL 0300643 W NL0300643 W NL 0300643W WO 2004026981 A1 WO2004026981 A1 WO 2004026981A1
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WO
WIPO (PCT)
Prior art keywords
polyester
composition according
carboxyl
composition
hydroxy alkyl
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/NL2003/000643
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English (en)
Inventor
Johannes Groen
Willem Grisnich
Menno Ferdinand Hierden Van
Cornelis Albertus Joannes Joseph Rossum Van
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.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
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 IP Assets BV filed Critical DSM IP Assets BV
Priority to AU2003265011A priority Critical patent/AU2003265011A1/en
Publication of WO2004026981A1 publication Critical patent/WO2004026981A1/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

Definitions

  • the invention relates to a binder composition comprising at least one carboxyl functional polyester and at least one ⁇ -hydroxy alkyl amide.
  • the invention also relates to a coating composition comprising such a binder composition, a process for the preparation of a binder composition, a process for coating a substrate with the coating composition, the coated substrate and its use.
  • thermosetting powder-paint composition comprises a carboxyl group or anhydride group containing polymer and a linear or branched condensation polymer with at least one hydroxy alkyl amide endgroup, that is preferably a ⁇ -hydroxy alkyl amide.
  • thermosetting powder-paint compositions are cured into a coating by means of a circulation oven at a minimum temperature of 180°C and for the duration of 15 minutes. Shorter durations are possible, however a higher temperature must compensate for the shorter time.
  • a drive exists towards lower curing temperatures. This drive is dictated by the need to lower the costs of the coating process. However the lower curing temperatures must be compensated for by an increase in curing time to obtain sufficient mechanical properties of the final coating. An increase in time would lead to a reduction in output of an existing coating plant. To obtain the same output the capacity should be increased by investments in hardware, which is not desirable from an economic point of view.
  • coating systems that comprise linear carboxyl functional polyesters and ⁇ -hydroxy alkyl amides.
  • the carboxyl functional polyesters are synthesized from specified bifunctional monomeric carboxylic acids and bifunctional alcohols.
  • the carboxylic acid used is a mixture of at least isophthalic acid and at least one other specified dicarboxylic acid.
  • the alcohol is a mixture from at least one branched aliphatic diol and at least one other further specified alcohol.
  • the obtained polyesters can be cured at a temperature of 180°C during 10 minutes by using Primid® XL 552 (EMS), a ⁇ -hydroxy alkyl amide compound.
  • EMS Primid® XL 552
  • a disadvantage of the coating systems based on these components is that the color of the obtained coatings after the curing cycle is not satisfactory, because the coating suffers of yellowing. This phenomenon especially occurs when the curing of the coating takes place in a gas-oven.
  • a binder composition comprising at least one carboxyl functional polyester and at least one ⁇ - hydroxy alkyl amide, which can be cured in 10 minutes at a temperature of 180°C while resulting in a coating with improved colour properties and sufficient mechanical properties.
  • a binder composition comprising at least one carboxyl functional polyester and at least one ⁇ -hydroxy alkyl amide, wherein at least one of the carboxyl functional polyesters is a modified polyester wherein the modification of the polyester has taken place with a salt-forming phosphorus compound.
  • a further additional advantage is that the amount of anti-oxidant that is necessary in the coating composition according to the invention can be lower than with coating compositions in the prior art, while retaining good properties.
  • a lower level of anti-oxidant is not only from an economic point of view very interesting; it is also from an environmental point of view important. Some anti-oxidants have in the long range a detrimental effect on the environment, especially the aquatic environment. Therefore any possibility to decrease the amount of such a compound is very desirable.
  • binder composition is meant the total of resins and crosslinkers.
  • coating composition is meant the binder composition with the pigments and additives.
  • coating is meant the paint after curing.
  • the binder composition according to the invention comprises at least one carboxyl functional modified polyester wherein the modification of the polyester has taken place with a salt-forming phosphorus compound.
  • the binder composition according to the invention can in addition to this carboxyl-functional modified polyester comprise other resins either modified or not. Examples of other suitable resins are polyurethanes, polyacrylates, polyesters. When other resins are combined with the carboxyl-functional modified polyester, preferably polyesters are used. Preferably these polyesters are also carboxyl-functional modified polyesters as in that case best results are obtained in relation to the reactivity combined with the color.
  • the binder composition according to the invention comprises at least one ⁇ -hydroxy alkyl amide.
  • the binder composition according to the invention can in addition to this ⁇ -hydroxy alkyl amide comprise other ⁇ -hydroxy alkyl amides.
  • the binder composition according to the invention comprises the at least one carboxyl functional polyester and the at least one ⁇ -hydroxy alkyl amide in a certain ratio to obtain in the end a suitable coating.
  • This ratio, Q is defined in formula I:
  • K is the number of carboxylgroups on the modified polyester
  • L is the number of phosphorus derived groups on the modified polyester that are reactive towards the hydroxy groups on the ⁇ -hydroxy alkyl amide
  • M is the number of the hydroxy groups on the ⁇ -hydroxy alkyl amide.
  • the ratio Q is preferably between 0,5 and 1 ,5, more preferred between 0,75 and 1 ,25.
  • the amount of modifying agent is chosen in such a way to reach the desired level.
  • the person skilled in the art can, without undue burden, easily perform this.
  • Preferably between 0,1 and 5 w% phosphorus based on the weight of the modified polyester is present. With a too low level of phosphorus present the reactivity is not increased enough to be able to cure the coating composition in a short time at a relatively low temperature. With a too high level of phosphorus the appearance of the final surface after curing is not satisfactory. With more preference between 0,25 and 3 w% phosphorus based on the weight of the modified polyester is present. Most preferred is a range between 0,5 and 2 w%.
  • the carboxyl-functional modified polyester can be prepared according to methods known to the person skilled in the art, for example in a one-step or two-step process.
  • a hydroxyl-functional polyester is prepared according to known methods and in a second step the hydroxyl-functional polyester is modified with both a suitable amount of salt-forming phosphorus compound and a compound able to convert a hydroxyl-functional polyester into a carboxyl- functional polyester, to obtain the carboxyl-functional modified polyester according to the invention.
  • the compound able to convert a hydroxyl-functional polyester into a carboxyl-functional polyester is a compound that has groups that are reactive towards hydroxyl-groups and that has in addition to those groups at least one carboxyl-group, for example trimellitic anhydride.
  • the modification of the hydroxyl-functional polyester results in a carboxyl-functional polyester wherein part of the hydroxyl groups has been replaced by phosphorus containing groups and the other part of the hydroxyl groups has been turned into carboxyl groups.
  • the phosphorus containing groups can be located either in the backbone of the polyester or in the side chains of the polyester.
  • a hydroxyl-functional polyester can for example be obtained by causing polyhydric alcohols to react with acids or acid anhydrides by choosing a certain molar ratio of the polyhydric alcohols and the acids or acid anhydrides. This ratio may vary for example between 1.2:1.0 and 1.0:1.0 for the preparation of the hydroxyl-functional polyester.
  • Suitable polyhydric alcohols for the preparation of the polyester can have an aliphatic or aromatic nature.
  • Suitable aliphatic polyhydric alcohols for preparing the hydroxyl-functional polyesters have a functionality of at least two and can contain from 2-24 carbon atoms. They include for example ethylene glycol, diethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 2,2,4-trimethylpentanediol-(1 ,3), 1 ,6-hexanediol, neopentyl glycol, 2-methyl-1 ,3- propanediol, 2-ethyl-2-butyl-1 ,3-propanediol, trimethylpentanediol, hydroxypivalic neopentyl glycol ester, tricyclodecane dimethanol, cyclohexane dimethanol, hydrogenated diphenylol
  • NPG neopentyl glycol
  • TMP trimethylolpropane
  • Suitable aromatic polyhydric alcohols for preparing the hydroxyl- functional polyesters have a functionality of at least two and can contain from 2-24 carbon atoms. They include for example bisphenol A bis(hydroxyethyl) ether.
  • Suitable aliphatic polybasic carboxylic acids for preparing the polyesters have a functionality of at least two and can contain from 2-36 carbon atoms. They can have a straight or branched chain. Preferably aliphatic polybasic carboxylic acids are used with 6-16 carbon atoms.
  • adipic acid for example adipic acid, fumaric acid, sebacic acid, tetrahydrophthalic acid, hexahydroterephthalic acid, decane dicarboxylic acid, succinic acid, maleic acid, hexahydrophthalic acid, azelaic acid and/or dimerised fatty acids or their corresponding acid anhydrides for example tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride and/or hexahydrophthalic anhydride.
  • Suitable aromatic polybasic carboxylic acids for preparing the polyesters have a functionality of at least two and can contain from 2-36 carbon atoms.
  • aromatic polybasic carboxylic acids are used with 6-16 carbon atoms. They include for example phthalic acid, isophthalic acid and/or terephthalic acid, dimethyl terephthalate ester or acid anhydrides for example phthalic anhydride, trimellitic anhydride, 1 ,8-naphthalic anhydride and pyromellitic anhydride.
  • isophthalic acid or terephthalic acid is used.
  • aliphatic and aromatic polybasic carboxylic acids are suitable, it is preferred to use a polyester that doesn't contain adipic acid derived building blocks in the polyester chain. It is even more preferred to use a polyester that doesn't contain aliphatic acid derived building blocks. It was surprisingly found that with these preferred polyesters the flow is improved. Additionally also better mechanical properties were obtained. When not all objects of the present invention as described above need to be reached at the same time, but the main object is to improve the mechanical properties also carboxyl functional polyesters without adipic acid (and more generally without aliphatic acid) derived building blocks and without phosphorous modification can be used.
  • the carboxyl-functional modified polyester preferably contains at least one aromatic monomer, either the acid or the alcohol.
  • the glass temperature should be high enough.
  • a high glass temperature can be reached by incorporating monomers with an aromatic character into the polyester chain.
  • the polyester according to the invention can be branched by incorporating tri- or more functional polycarboxylic acids or the corresponding anhydrides and/or tri- or more functional polyol components in an amount of at most 15 mol %, preferably between 6 and 12 mol % to the total acid component or polyol component. These branched polyesters result in an improved adhesion and flexibility of the finally cured coating.
  • the esterification reaction in the polyester synthesis is carried out under conditions well-known to the man skilled in the art. Preferably the reaction is carried out in a nitrogen atmosphere at temperatures of between 180 S C and 260 Q C.
  • the polyester-forming reaction can take place in the presence of one or more catalysts.
  • suitable catalysts are dibutyl tin oxide, tin chloride, butyl chlorotin dihydroxide (FASCAT®) or tetrabutyloxytitanate.
  • the reaction water released during the reaction can be removed by distillation.
  • the desired degree of esterification is reached by means of azeotropic distillation or vacuum in the last phase.
  • the carboxyl-functional modified polyester is obtained by modification of the hydroxyl-functional polyester with a salt-forming phosphorus compound.
  • Suitable salt-forming phosphorus compounds include for example phosphoric acid, phosphorous acid, phosphinic acid, phenylphosphinic acid, phosphinous acid, organic acid phosphate, phosphorous oxychloride, alkyl esters of phosphoric acid, anhydrides of phosphoric acid, hydrogen containing salts of phosphoric acid, hypo-phosphorous acid and mixtures thereof for example tri-butylphosphite.
  • phosphoric acid is used.
  • the binder composition according to the invention comprises in addition to the at least one carboxyl-functional polyester at least one ⁇ -hydroxy alkyl amide.
  • the carboxyl groups on the polyester can react with the functional ( ⁇ -hydroxy) groups on the ⁇ -hydroxy alkyl amide to form a network.
  • the ⁇ -hydroxy alkyl amide is preferably a linear or branched condensation polymer containing ester groups and at least one amide group in the backbone, having at least one hydroxy alkyl amide endgroup and having a weight average molecular mass of > 800 g/mol.
  • the ⁇ -hydroxy alkyl amide with a weight average molecular mass of > 800 g/mol has at least two groups according to formula II:
  • R 4 R 6 I I Y C— C— O— H , H, (C C 24 )(cyclo)alkyl or (C 6 -C 10 ) aryl,
  • R 5 H B (C 2 -C 24 ), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may, independently of one another, be the same or different, H, (C 6 -C ⁇ o) aryl or (C- ⁇ -C 8 )(cyclo)alkyl radical.
  • the ⁇ -hydroxy alkyl amide has at least two groups according to formula II wherein R 3 and R 6 are both methyl, R 1 , R 2 , R 4 , R 5 all are hydrogen and B is C 6 H 4 -diradical.
  • the binder composition according to the invention can, in principle, be used in all kinds of coating systems. However it is advantageously used in powder coating systems.
  • the performance and the characteristics of the finally obtained powder coating after curing of the coating composition are influenced by several factors.
  • the glass transition temperature of the binder plays an important role in the (storage) stability of the powder coating composition. In case the glass transition temperature is low the mobility of the components in the powder coating composition is relatively high, resulting in a system that is not powder stable. As a consequence the powder coating composition cannot be stored for a considerable time.
  • the necessary glass temperature for a certain powder coating composition depends on the storage conditions. In countries with a relatively high ambient temperature binders with a higher glass transition temperature are needed.
  • the glass transition temperature (T g ) of the powder coating should not be lower than 40 S C.
  • Another factor of influence for the behavior of a powder coating composition is the particle size. The smaller the particles, the better the leveling of the coating. Also the amount of pinholes, orange peel and shrinkage during curing are positively influenced when using smaller particles.
  • the person skilled in the art of powder coatings knows or can without undue experimentation determine the most suitable parameters for a powder coating composition.
  • the invention also relates to a process for the preparation of a binder composition according to the invention, wherein at least one carboxyl-functional modified polyester is combined with at least one ⁇ -hydroxy alkyl amide in a mixing device.
  • a mixing device is operated at a temperature below 160°C.
  • the coating composition according to the invention will generally contain at least one component chosen from the list comprising pigments, antioxidants, hindered amine light stabilizers, degassing agents, fillers and/or wetting agents.
  • the coating composition according to the invention is generally applied onto a substrate.
  • the substrate is not particularly critical, examples are aluminum and (phosphatized) steel. It is in particular the temperature at which the curing takes place that determines whether the substrate is suitable or not. Some substrates, generally referred to as the heat-sensitive substrates, are less suitable as a higher risk exists that the substrate itself will deteriorate in some way or another.
  • the invention also relates to a process for coating a substrate with a coating composition according to the invention by applying the coating composition onto the substrate and curing it.
  • the coating composition can be applied by means known to the person skilled in the art, reference can for example be made to "Powder Coatings, Chemistry and Technology" by T.A. Misev, John Wiley & Sons, 1991 , page 324-349.
  • a corona charging gun or tribo charging gun can be made by a corona charging gun or tribo charging gun.
  • Curing can be effected through various means, for example thermal curing, electron beam curing and/or UV-curing.
  • Thermal curing can take place in various types of ovens, for example gas oven, electrical oven or infrared oven. Preferably the curing takes place at a temperature of maximally 180°C and during a time of maximally 10 minutes.
  • the substrate in general can be wholly or partly coated depending on its use.
  • the invention also relates to the wholly or partly coated substrate wherein the coating is obtained by the process according to the invention.
  • the wholly or partly coated substrates according to the invention can be used for both indoor and outdoor applications.
  • the monomers for the second step trimellitic acid and phosphoric acid, were added at a temperature of 180°C. The temperature was then raised to 225°C. When setpoint was reached pull vacuum and after 5 minutes adjusted the setpoint on 195°C. Additionally the viscosity was determined to be 40 with a Rheomat Plate Plate viscosimeter (Pa.s, at 160°C). The acid value was determined to be 84 mg KOH/g.
  • the monomers for the second step trimellitic acid and phosphoric acid, were added at a temperature of 180°C. The temperature was then raised to 225°C. When setpoint was reached pull vacuum and after 5 minutes adjust the setpoint on 195°C. Additionally the viscosity was determined to be 20 with a
  • the monomer for the second step trimellitic acid
  • trimellitic acid was added at a temperature of 180°C.
  • the temperature was then raised to 225°C.
  • the viscosity was determined to be 16 with a Rheomat Plate Plate viscosimeter (Pa.s, at 160°C).
  • the acid value was determined to be 74 mg KOH/g.
  • the monomer for the second step trimellitic acid
  • trimellitic acid was added at a temperature of 180°C.
  • the temperature was then raised to 225°C.
  • setpoint was reached, after one hour the viscosity was determined to be 26 with a
  • Example l-lll and Comparative Example A Preparation of a coating composition
  • Powder paint compositions were prepared consisting of a ⁇ -hydroxy alkyl amide resin as described in Experiment I of WO 01/68781 , pigment and or filler (see table 5), Resiflow® PV5 (flow agent) and degassing agent benzoin. This powder composition was added to the granulated polyester resin according to Experiment I, II, III or Comparative Experiment A respectively. The amounts of the ingredients of the coating compositions are shown in Table 5.
  • the powder paint was prepared by mixing and extrusion in a PRISM extruder at 120°C.
  • the composition was ground in the usual manner.
  • the extrudate was cooled, milled and sieved and the fraction with particle size between 50-90 ⁇ m was collected and used as the powder paint.
  • the powder paint was electrostatically sprayed (Corona) onto aluminium test panels (AI-46). After a cure of 10 minutes at 180°C in a circulation oven the panels were tested.
  • Table 5 Powder paint composition and test results
  • TMA trimellitic anhydride
  • Acid value is determined in mg KOH/g polyester
  • Reversed Impact is determined with 60 inchpound at an AI-46 substrate

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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)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne une composition de liant comprenant au moins un polyester à fonction carboxyle et au moins un β-hydroxy alkylamide, caractérisée en ce qu'au moins un des polyesters à fonction carboxyle est un polyester modifié à fonction carboxyle, dont la modification a été effectuée avec un composé phosphoré formant un sel.
PCT/NL2003/000643 2002-09-17 2003-09-16 Composition de liant comprenant un polyester a fonction carboxyle et un $g(b)-hydroxy alkylamide Ceased WO2004026981A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003265011A AU2003265011A1 (en) 2002-09-17 2003-09-16 BINDER COMPOSITION COMPRISING A CARBOXYL FUNCTIONAL POLYESTER AND A Beta-HYDROXY ALKYL AMIDE

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP02078849.3 2002-09-17
EP02078849 2002-09-17

Publications (1)

Publication Number Publication Date
WO2004026981A1 true WO2004026981A1 (fr) 2004-04-01

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PCT/NL2003/000643 Ceased WO2004026981A1 (fr) 2002-09-17 2003-09-16 Composition de liant comprenant un polyester a fonction carboxyle et un $g(b)-hydroxy alkylamide

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AU (1) AU2003265011A1 (fr)
WO (1) WO2004026981A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013017606A1 (fr) 2011-08-04 2013-02-07 Akzo Nobel Coatings International B.V. Composition de revêtement en poudre thermodurcissable durable
WO2021144061A1 (fr) 2020-01-13 2021-07-22 Dsm Ip Assets B.V. Microparticules non poreuses

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1134266A1 (fr) * 2000-03-13 2001-09-19 Dsm N.V. Composition de peinture en poudre

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1134266A1 (fr) * 2000-03-13 2001-09-19 Dsm N.V. Composition de peinture en poudre

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013017606A1 (fr) 2011-08-04 2013-02-07 Akzo Nobel Coatings International B.V. Composition de revêtement en poudre thermodurcissable durable
US9365740B2 (en) 2011-08-04 2016-06-14 Akzo Nobel Coatings International B.V. Thermosetting durable powder coating composition
US9868813B2 (en) 2011-08-04 2018-01-16 Akzo Nobel Coatings International B.V. Thermosetting durable powder coating composition
WO2021144061A1 (fr) 2020-01-13 2021-07-22 Dsm Ip Assets B.V. Microparticules non poreuses

Also Published As

Publication number Publication date
AU2003265011A1 (en) 2004-04-08

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