GB2290795A

GB2290795A - Polyester resin powder coating compositions

Info

Publication number: GB2290795A
Application number: GB9510945A
Authority: GB
Inventors: John Ridland
Original assignee: Tioxide Specialties Ltd
Current assignee: Tioxide Specialties Ltd
Priority date: 1994-06-28
Filing date: 1995-05-31
Publication date: 1996-01-10
Anticipated expiration: 2015-05-31
Also published as: GB2290795B; GB9510945D0

Abstract

A method of curing a polyester powder coating composition comprises reacting the polyester resin with an alkanolamine derivative of titanium or zirconium. This derivative is the reaction product of an orthoester or a condensed orthoester of titanium or zirconium with a trialkanolamine and with a dialkanolamine or a monoalkanolamine. In the reaction product the ratio of trialkanolamino radicals to Ti or Zr atoms is from 0.5:1 to 1.5:1 and the ratio of monoalkanolamino radicals or dialkanolamino radicals to Ti or Zr atoms is from 0.2:1 to 2.0:1. The reaction products are preferably derivatives of ethanolamines or isopropanolamines and can be used to cure carboxyl-rich resins or hydroxyl-rich resins.

Description

POLYESTER RESIN POWDER COATING COMPOSITIONS This invention relates to powder coating compositions based on polyester resins and in particular to the use of certain organotitanium or organozirconium compounds to cure polyester resin powder coating compositions.

Coating compositions comprising powdered thermo-setting compositions are increasingly used for the formation of highly durable and decorative finishes. Such compositions, usually known as powder coating compositions are frequently based on polyester resins which can be prepared by the reaction of polyhydric alcohols and polybasic acids and in which the molar ratio of alcohol to acid can be adjusted to produce resins which contain an excess of hydroxyl groups over acid groups (hydroxyl-rich resins) or resins which contain an excess of acid groups over hydroxyl groups (carboxyl-rich resins).

The carboxyl-rich resins are frequently cured by cross-linking with an isocyanurate such as triglycidyl isocyanurate (TGIC) to produce durable coatings ideally suitable for exterior use. However, there is now a desire to reduce the use of triglycidyl isocyanurate.

Cross-linking of carboxyl-rich resins with epoxy resins such as resins based on bisphenol A is known to produce resins which are frequently called hybrid resins. However these resins do not possess the same properties or exterior durability as those produced by cross-linking with triglycidyl isocyanurate.

Coatings having good exterior durability can also be produced by crosslinking hydroxyl-rich resins with isocyanates. These isocyanates may be blocked, for example with caprolactam, to prevent premature reaction with the polyester. However, there is now a general trend within the coating industry to avoid the use of caprolactam-blocked isocyanates when possible.

Our co-pending application GB 9408430.8 discloses a method of curing polyester powder coatings using specified organotitanium or organozirconium compounds which are derivatives of a trialkanolamine.

It has now been found, surprisingly, that certain organotitanium or organozirconium compounds derived from monoalkanolamines or dialkanolamines in addition to trialkanolamines are useful as curing agents for polyester powder coating compositions.

Accordingly, a method of curing a powder coating composition comprises reacting a polyester resin with an organotitanium compound or an organozirconium compound which is the reaction product of an orthoester or a condensed orthoester of titanium or zirconium with a trialkanolamine and with a monoalkanolamine or a dialkanolamine, said reaction product having a ratio oftrialkanolamino radicals to titanium or zirconium atoms of from 0.5:1 to 1.5:1 and a ratio of monoalkanolamino radicals or dialkanolamino radicals to titanium or zirconium atoms of from 0.2:1 to 2.0:1.

The polyester resins which can be used in the method of the invention can be those which are described as hydroxyl-rich or those which are described as carboxyl-rich. They can be prepared from polybasic carboxylic acids or their esterifiable derivatives and from polyols by any suitable known process.

Polybasic acids which are useful for their preparation include aromatic, cycloaliphatic or aliphatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, adipic acid and sebacic acid. Esters of these acids with monohydric alcohols, for example dimethyl terephthalate or acid anhydrides such as phthalic anhydride can also be used as reactants for preparing the polyesters in place of the equivalent acid.

Suitable polyhydric alcohols include 1 ,2-ethanediol (ethylene glycol), 1,2-propanediol, trimethylolpropane, neopentyl glycol, 1,3-butanediol, 1,4butanediol, pentaerythritol, glycerol, tris(hydroxyethyl)isocyanurate and ethoxylated bisphenol A (2,2-bis[4,4'-hydroxyethoxyphenyl] propane).

Preferably the polyesters are branched and have a high melting point.

The molar ratio of the raw materials used for polyester production is selected so as to ensure an excess of either hydroxyl groups (hydroxyl-rich resins) or carboxyl groups (carboxyl-rich resins). Typically, hydroxyl-rich resins which are commercially available have a hydroxyl number between 20 and 150 mg KOH per gram. For the practice of this invention the preferred hydroxyl number is between 15 and 100 mg KOH per gram and more preferably between 15 and 60 mg KOH per gram. Such resins usually have an acid number of from 0 to 15 mg KOH per gram. Typical, commercially available, carboxyl-rich resins which are of use in the method of the invention have an acid number of from 15 to 100 mg KOH per gram and preferably from 15 to 60 mg KOH per gram and a hydroxyl number of less than 30 mg KOH per gram and preferably less than 10 mg KOH per gram.

Resins which are a copolymer of a polyester and another polymer are useful in the practice ofthe invention and such copolymers include copolymers of acrylic polymers containing carboxyl groups.

The titanium or zirconium compounds which are of use in the method of the invention are derivatives of at least two alkanolamines. One of these alkanolamines is a trialkanolamine which can be represented by the general formula N(ROH)3 and the other is a dialkanolamine [general formula HN(ROH)2] or a monoalkanolamine [general formula H2NROH]. In each of the formulae, R represents a divalent radical, preferably containing up to 3 carbon atoms. More preferably, R is -CH2-CH2- or -CH(CH)CH2-. When R represents one of these radicals the trialkanolamine is triethanolamine or triisopropanolamine, the dialkanolamine is diethanolamine or diisopropanolamine and the monoalkanolamine is monoethanolamine or monoisopropanolamine.Usually, but not necessarily, an organotitanium or organozirconium compound useful in the invention will be derived from a trialkanolamine and another alkanolamine wherein R represents the same group in each alkanolamine.

The titanium or zirconium compounds are characterised by the proportions of trialkanolamino radicals and monoalkanolamino or dialkanolamino radicals present in the reaction product. The ratio of trialkanolamino radicals to titanium or zirconium atoms is from 0.5:1 to 1.5:1 and preferably from 1.0:1 to 1.5:1.

The ratio of monoalkanolamino or dialkanolamino radicals to titanium or zirconium atoms is from 0.2:1 to 2.0:1 and preferably from 0.3:1 to 1.0:1.

The organotitanium or organozirconium compounds are reaction products of alkanolamines with a titanium or zirconium orthoester or a condensed orthoester of titanium or zirconium. The orthoesters can be represented by the formula M(OR')4 and the condensed orthoesters by the formula R'-[OM(OR')2] X-OR' in which M represents titanium or zirconium, R' is an alkyl radical or a radical containing one or more ether linkages and x is an integer. The condensed orthoesters can be prepared by controlled hydrolysis of orthoesters. Usually, R' contains up to 8 carbon atoms and preferably up to 6 carbon atoms. Preferably x is from 2 to 4.Suitable examples of orthoesters or condensed orthoesters include tetraisopropoxy titanium, tetraethoxy titanium, tetra-n-butoxy titanium, tetrakis(2-ethylhexoxy) titanium, tetrakis (2-ethoxyethoxy) titanium, polybutyl titanate, tetra-n-propoxy zirconium and tetra-n-butoxy zirconium.

The organotitanium or organozirconium compounds can be readily prepared by reaction of chosen alkanolamines with a titanium or zirconium orthoester or condensed orthoester in an appropriate molar ratio followed by the removal of alcohol which is displaced. For example, reaction of 3 moles of triethanolamine and 2 moles of diethanolamine with 3 moles of tetraisopropoxy titanium followed by removal of isopropyl alcohol generated produces an organotitanium compound suitable for use in the method of the invention.

The quantity of organotitanium or organozirconium compound used in the method of the invention depends on, amongst other factors, the desired degree of cross-linking of the polyester resin and the nature of the polyester resin. Generally, from 2 to 20 per cent by weight is used and preferably the quantity is from 5 to 8 per cent by weight based on weight of resin.

Before curing the powder coating composition the organotitanium or organozirconium compound is thoroughly mixed with the polyester resin.

Typically, the resin and organotitanium or organozirconium compound, together with other ingredients such as pigments and flow modifiers are firstly mixed as a powder in a high intensity mixer such as Henschel mixer. Suitable pigments include inorganic pigments such as titanium dioxide and iron oxide and organic pigments such as carbon black and phthalocyanine blue. In addition inorganic extenders such as barium sulphate or calcium carbonate may be added as part of the pigmentary system. Compounds which are useful as flow modifiers include silicones and polyacrylates such as polybutyl acrylate and butyVethylhexyl acrylate copolymers.

The mixed powder is usually subsequently fed to an extruder of a type conventionally used for powder coating compositions such as a Buss-Ko Kneader PR46. The extruder forms a semi-molten mass from the mixed powder at a temperature of about 90"C to 1200C and this extrudate is cooled to form a brittle solid which is then pulverised in a suitable mill such as a pin mill, to produce a powder coating composition. Usually the powder coating is sieved before application to ensure the absence of oversized particles.

In use the powder coating composition is coated on to the surface to be treated in any convenient manner. For the treatment of aluminium or steel, for example, electrostatic spraying is commonly employed as this technique produces a very uniform coating even on inaccessible surfaces. An alternative technique which is extremely useful is triboelectric spraying.

The coated surface is then heated to a sufficiently high temperature to allow the resin to coalesce and cure by cross-linking the free hydroxyl or carboxyl groups in the polyester resin by means of the organotitanium or organozirconium compound. The temperature at which the resin is cured depends to some extent upon the glass transition temperature and the softening point of the resin and the reactivity of the cross-linking agent but generally is in the range 140"C to 220"C. The resin is normally fUlly cured by heating at a temperature in this range for a period of between 5 and 30 minutes, more usually between 5 and 20 minutes.Typical curing schedules for carboxyl-rich polymers are 15 to 20 minutes at 1600C, 10 to 20 minutes at 1800C or 6 to 10 minutes at 200"C. For hydroxyl-rich resins typical schedules are 15 to 20 minutes at 1900C or 10 to 15 minutes at 200"C.

A number of well-known tests are used to assess the quality of the finished coating. Typically, a methyl ethyl ketone double-rub test is used to assess the degree of cure and reverse impact and bend tests are used to confirm the degree of cross-linking and to assess the integrity of the coating and its bonding to the coated surfaces. Colour and gloss of the finished coatings are also important properties of the cured resin.

The coatings cured according to the method ofthe current invention are of acceptable quality when assessed by these tests. The organotitanium and organozirconium compounds are active cross-linkers which are solid and have a low volatility.

The invention is illustrated by the following examples.

EXAMPLE 1 Triethanolamine (447.6g, 3 moles) and diethanolamine (105.1 lg, 1 mole) were added to tetraisopropoxy titanium (852g, 3 moles) in a rotary evaporator flask and mixed for 10 minutes under nitrogen. The solution was heated under vacuum to remove isopropanol and yield a yellow resinous solid having a titanium content of 17.53% by weight.

EXAMPLE 2 Triethanolamine (447.6g, 3 moles) and diethanolamine (210.2g, 2 moles) were added to tetraisopropoxy titanium (852g, 3 moles) in a rotary evaporator flask and mixed for 10 minutes under nitrogen. The solution was heated under vacuum to remove isopropanol and yield a yellow resinous solid having a titanium content of 16.37% by weight.

EXAMPLE 3 Triethanolamine (74.6g, 0.5 moles) and monoethanolamine (10.2g, 0.17 moles) were added to tetraisopropoxy titanium (142g, 0.5 moles) in a rotary evaporator flask and mixed for 5 minutes under nitrogen. The solution was heated under vacuum to remove isopropanol and yield a yellow resinous solid having a titanium content of 19.01% by weight.

EXAMPLE 4 Triethanolamine (74.6g, 0.5 moles) and monoethanolamine (20.3g, 0.33 moles) were added to tetraisopropoxy titanium (142g, 0.5 moles) in a rotary evaporator flask and mixed for 5 minutes under nitrogen. The solution was heated under vacuum to remove isopropanol and yield a yellow resinous solid having a titanium content of 17.54% by weight.

EXAMPLE 5 Reactivity Test The reactivity of the organotitanium or organozirconium cross-linkers towards polyester resins can be simply checked using a gel time test. 7 parts cross-linker were ground with 93 parts polyester resin (see Table 1) with a mortar and pestle. Approximately 0.7g of this mixture was placed in a depression in a thermostatically controlled heated aluminium block. The temperature was preset to 200"C. The molten mixture was stirred with a wooden cocktail stick and the time in seconds noted for gelation (snapback of molten thread) to occur. When gelation did not occur within 360 seconds the appearance ofthe resin after 360 seconds was noted and is described in Table 2.

TABLE 1

RESIN OII Value Acid Value Viscosity at 165 C Uralac P2400 (1) - 30-37 mg/KOH/g 700 dPa.s Uralac P2115 (1) 30-45 10 max mg/KOH/g 550 dPa.s Neocrest P660 (2) - 2840 mgfKOHfg (1) Supplied by DSM resins (2) Supplied by Zeneca resins TABLE 2

Product of Gel time (secs) at 200 C Example No. P2115 P2400 P660 1 210 190 155 2 No gel 325 200 3 255 180 270 4 270 240 285

Claims

CLAIMS 1. A method of curing a powder coating composition comprising reacting a polyester resin with an organotitanium compound or an organozirconium compound which is the reaction product of an orthoester or a condensed orthoester of titanium or zirconium with a trialkanolamine and with a monoalkanolamine or a dialkanolamine, said reaction product having a ratio oftrialkanolamino radicals to titanium or zirconium atoms of from 0.5:1 to 1.5:1 and a ratio of monoalkanolamino radicals or dialkanolamino radicals to titanium or zirconium atoms of from 0.2:1 to 2.0:1.
2. A method according to claim 1 in which the trialkanolamine is triethanolamine or triisopropanolamine.
3. A method according to claim 1 or 2 in which the dialkanolamine is diethanolamine or diisopropanolamine.
4. A method according to any one of the preceding claims in which the monoalkanolamine is monoethanolamine or monoisopropanolamine.
5. A method according to any one of the preceding claims in which the trialkanolamine has the formula N(ROH)3, the dialkanolamine has the formula HN(ROH)2 and the monoalkanolamine has the formula H2NROH wherein, in each formula, R represents a divalent radical, said divalent radical being the same in each of the alkanolamines used in the method.
6. A method according to any one of the preceding claims in which the ratio of trialkanolamino radicals to titanium or zirconium atoms is from 1.0:1 to 1.5:1.
7. A method according to any one of the preceding claims in which the ratio of monoalkanolamino or dialkanolamino radicals to titanium or zirconium atoms is from 0.3:1 to 1.0:1.
8. A method according to any one of the preceding claims in which the orthoester ester of titanium or zirconium is represented by the formula M(OR')4 and the condensed orthoester is represented by the formula R'-[OM(OR')2]X-OR' wherein, in each formula, M represents titanium or zirconium, R' is an alkyl radical or a radical containing one or more ether linkages and containing up to eight carbon atoms and x is an integer.
9. A method according to claim 8 in which RI contains up to 6 carbon atoms.
10. A method according to claim 8 or 9 in which x is an integer from 2to4.
11. A method according to any one of the preceding claims in which the orthoester or condensed orthoester is tetraisopropoxy titanium, tetraethoxy titanium, tetrakis(2-ethylhexoxy) titanium, tetrakis(2-ethoxyethoxy) titanium, polybutyl titanate, tetra-n-propoxy zirconium or tetra-n-butoxy zirconium.
12. A method according to any one of the preceding claims in which the polyester resin is an ester of terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, adipic acid or sebacic acid.
13. A method according to any one of the preceding claims in which the polyester resin is an ester of 1 ,2-ethanediol, 1 2-propanediol, trimethylolpropane, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, pentaerythritol, glycerol, tris(hydroxyethyl) isocyanurate or ethoxylated bisphenol A.
14. A method according to any one of the preceding claims in which the polyester resin is a hydroxyl-rich resin having a hydroxyl number in the range 20 to 150 mg KOH per gram.
15. A method according to claim 14 in which the hydroxyl number of the polyester resin is in the range 15 to 100 mg KOH per gram.
16. A method according to claim 14 or 15 in which the hydroxyl number of the polyester resin is in the range 15 to 60 mg KOH per gram.
17. A method according to any one of claims 14 to 16 in which the polyester resin has an acid number in the range 0 to 15 mg KOH per gram.
18. A method according to any one of claims 1 to 13 in which the polyester resin is a carboxyl-rich resin having an acid number in the range 15 to 100 mg KOH per gram.
19. A method according to claim 18 in which the acid number of the polyester resin is in the range 15 to 60 mg KOH per gram.
20. A method according to claim 18 or 19 in which the polyester resin has a hydroxyl number of less than 30 mg KOH per gram.
21. A method according to claim 20 in which the hydroxyl number of the polyester resin is less than 10 mg KOH per gram.
22. A method according to any one of the preceding claims in which the polyester resin is a copolymer of an acrylic polymer containing carboxyl groups.
23. A method according to any one of the preceding claims in which the organotitanium compound or organozirconium compound is present in an amount in the range 2 to 20 per cent by weight based on weight of resin.
24. A method according to claim 23 in which the amount of organotitanium compound or organozirconium compound is in the range 5 to 8 per cent by weight based on weight of resin.
25. A method according to any one of the preceding claims in which the powder coating composition is cured by reacting the polyester resin with the organotitanium or organozirconium compound at a temperature in the range 140"C to 220"C.
26. A method according to claim 25 in which the powder coating composition is cured for a period in the range 5 to 30 minutes.
27. A method according to claim 25 or 26 in which the powder coating composition is cured for a period in the range 5 to 20 minutes.
28. A method according to any one of the preceding claims in which the powder coating composition contains a carboxyl-rich polyester resin and is cured by heating for between 15 and 20 minutes at 160"C.
29. A method according to any one of claims 1 to 27 in which the powder coating composition contains a carboxyl-rich polyester resin and is cured by heating for between 10 and 20 minutes at 180"C.
30. A method according to any one of claims 1 to 27 in which the powder coating composition contains a carboxyl-rich polyester resin and is cured by heating for between 6 and 10 minutes at 200"C.
31. A method according to any one of claims 1 to 27 in which the powder coating composition contains a hydroxyl-rich resin and is cured by heating for between 15 and 20 minutes at 1900C.
32. A method according to any one of claims 1 to 27 in which the powder coating composition contains a hydroxyl-rich resin and is cured by heating for a period between 10 and 15 minutes at 200"C.
33. A method according to any one of the preceding claims in which a pigment, an extender or a flow modifier is mixed with the polyester resin and the organotitanium compound or organozirconium compound before the powder coating compositon is cured.
34. A method according to claim 33 in which the pigment is titanium dioxide, iron oxide, carbon black or phthalocyanine blue.
35. A method according to claim 33 in which the extender is barium sulphate or calcium carbonate.
36. A method according to claim 33 in which the flow modifier is a silicone, polybutyl acrylate or a copolymer of butyl acrylate and ethylhexyl acrylate.
37. A method according to any one ofthe preceding claims in which the polyester resin is mixed with the organotitanium compound or organozirconium compound and the mixture so formed is extruded at a temperature of 90"C to 1200C and subsequently pulverised.
38. A method according to any one of the preceding claims in which the powder coating composition is applied to a substrate by electrostatic spraying or triboelectric spraying before curing.
39. A composition suitable for use as a powder coating comprising a mixture of a polyester resin and an organotitanium compound or organozirconium compound which is the reaction product of an orthoester or a condensed orthoester of titanium or zirconium with a trialkanolamine and with a monoalkanolamine or a dialkanolamine, said reaction product having a ratio oftrialkanolamino radicals to titanium or zirconium atoms of from 0.5:1 to 1.5:1 and a ratio of monoalkanolamino radicals or dialkanolamino radicals to titanium or zirconium atoms of from 0.2:1 to 20: 1.
40. A method according to claim 1 in which the organotitanium compound is a compound prepared according to one of the methods of Examples 1 to 4.
41. A composition according to claim 39 in which the organotitanium compound is a compound prepared according to one of the methods of Examples 1 to 4.