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MXPA98000846A - A method for improving the loading capacity of a coating composition in po - Google Patents

A method for improving the loading capacity of a coating composition in po

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Publication number
MXPA98000846A
MXPA98000846A MXPA/A/1998/000846A MX9800846A MXPA98000846A MX PA98000846 A MXPA98000846 A MX PA98000846A MX 9800846 A MX9800846 A MX 9800846A MX PA98000846 A MXPA98000846 A MX PA98000846A
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Mexico
Prior art keywords
carbon atoms
formula
alkyl
group
independently
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Application number
MXPA/A/1998/000846A
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Spanish (es)
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MX9800846A (en
Inventor
Stephen Laver Hugh
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Ciba Specialty Chemicals Holding Inc
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Publication of MX9800846A publication Critical patent/MX9800846A/en
Publication of MXPA98000846A publication Critical patent/MXPA98000846A/en

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Abstract

A method for improving the loading capacity of a powder coating composition containing an organic film-forming binder, this method comprises incorporating into the powder coating composition at least two different compounds containing a residue of the formula (A) (See Formula) as electron donors

Description

A METHOD FOR IMPROVING THE LOADING CAPACITY OF A POWDER COATING COMPOSITION This invention relates to a method for improving the loading capacity of a powder coating composition. When applying powder coatings on a substrate by electrostatic charging techniques, it is common practice to add to the powder coating formulation, a charge control agent, which is usually an electron donor, as shown by eigel in DE- A-3 600 395. In practice it has been found that sterically hindered amines are the additives of choice for polyesters (EP-A-371528). Compounds such as Tinuvin '"' 770 or Chimassorb ™ 944 have been found to be charge control agents in organic pigments for electrostatic image development as described in JP-A-60/188 958 (Derwent 85-279 382/45) and JP-A-60/188 959 (Derwent 85-279 383/45) Sterically hindered amines in powdery top coatings for automotive use are described in US Pat. No. 4 402 983. GB-A-2 267 499 describes 2,2,6,6-tetramethyl-piperidinyl derivatives as stabilizers for powder coating compositions.
Acid catalyzed lacquer systems contain 2, 6, 6-tetramethylpiperidinyl derivatives as light stabilizers, they are described in WO-A-92/12201. In more detail, the present invention relates to a method for improving the loading capacity of a powder coating composition containing an organic film-forming binder, this method comprising incorporating into the powder coating composition an effective amount of at least two different compounds containing a residue of the formula (A) as electron donors. The two different compounds contain a residue of the formula (A), preferably they are chosen from the group consisting of classes a) a compound of the formula (Ia) or (Ib) wherein AX is hydrogen, alkyl with l ß carbon atoms or alkenyl with 3 to 6 carbon atoms, if bx is 1, A2 is alkyl with 1 to 9 carbon atoms, if bx is 2, A2 is alkylen with 1 to 10 carbon atoms or a group of the formula wherein R is alkyl having 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, R 2 is alkylene having 1 to 10 carbon atoms and R 3 and R 4 independently of one another are alkyl having 1 to 4 carbon atoms, cyclohexyl or ethylcyclohexyl and if bx is 4, A2 is alkanediyl with 4 to 10 carbon atoms; H2C - CH - CH - CH2 (Ib) R R R R wherein the radicals R independently of one another are -COO- (alkyl having 1 to 20 carbon atoms) or a group with Ai which is as defined above; b) a compound of the formula (II) (») wherein A3 and A7 independently of each other are hydrogen or alkyl having 1 to 12 carbon atoms, At, Aβ and ß independently of each other are alkylene with 2 to 10 carbon atoms and Ti, T2, ts, T «, T5, Tß , T7 and T8 independently of each other are a group of the formula (III) wherein Aβ is hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms substituted with alkyl having 1 to 4 carbon atoms, phenyl or a group of the formula (IV) and A9 and Aio independently of each other are as defined c) a compound of the formula (V) where T9, Uncle and Tu independently of each other represent a group of the formula (III); d) a compound of the formula (VI) wherein An, A13, Ai * and A15 independently of each other are hydrogen, alkyl with 1 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms substituted with alkyl with 1 to 4 atoms of carbon, phenyl or a group of the formula (IV), Ax 2 is alkylene with 2 to 10 carbon atoms, cycloalkylene with 5 to 7 carbon atoms or alkylene with 1 to 4 carbon atoms-di (cycloalkylene with 5 to 7 carbon atoms), or the radicals Au, A? and A13, together with the nitrogen atom to which they are connected, form a 5- to 10-membered heterocyclic ring or A? "and AIB together with the nitrogen atom to which they are attached. bound, they form a heterocyclic ring of 5 to 10 members, 1% is a number of 2 to 50 and at least one of the radicals AI1 (A13, At4 and Ais is a group of the formula (IV); the formula (VII) wherein A6 is alkyl with 1 to 10 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms substituted with alkyl with 1 to 4 carbon atoms or phenyl, Ai7 is alkylene with 3 to 10 carbon atoms, AX8 is as defined for At and b3 is a number from 1 to 50; f) a product obtained by reacting an intermediate product, which is obtained by reacting a polyamine of the formula (Vlll-a) with cyanuric chloride, with a compound of the formula H, N - (CH 2) b 4, - NH - (CH2) b4"- NH - (CH2) b4", - NH2 (VlII-a) where 4, b4- and b4., independently of each other are a number of 2 to 12, A19 is hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms or phenyl and A20 is as defined for Ax; g) a compound of the formula (IX) wherein A2 ?, A22, A23, A24 and A25 independently of each other represent a direct bond or alkylene with 1 to 10 carbon atoms, A26 is as defined for Ax and g is a number from 1 to 50; h) is a compound of the formula (X) wherein TX2, TX3 and T14 independently of each other are a group of the formula (XI) - CH2 - CH - CH2 - L (XI) OH wherein L is a group of the formula (III); i) a compound of the formula (XII) wherein Aa, ee hydrogen or methyl, A2β is a direct bond or alkylene with 1 to 10 carbon atoms and b6 is a number of 2 to 50; j) a compound of the formula (XIII) wherein Aa »is as defined for At and A30 is hydrogen, alkyl having 1 to 12 carbon atoms or alkoxy with 1 to 12 carbon atoms; k) a compound of the formula (XIV) wherein A31 is alkyl with 1 to 24 carbon atoms and A32 is co or is defined for A, * and 1) a compound of the formula (XV) wherein A33 is as defined for Ax and A34 is alkyl having 1 to 20 carbon atoms or alkenyl with 2 to 20 carbon atoms. The two different compounds contain a residue of the formula (A), preferably they are not covered by the same class. Examples of alkyl having up to 24 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3 -dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1, 1,3, 3-tetramethyl-butyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethexyl, 1, 1 , 3-tr i et i lhexi lo, 1,1,3,3-tetramethylpentyl, noniio, decyl, undecyl, 1-methylundecyl, dodecyl and 1,1, 3,3,5, -hexamethylhexyl. One of the preferred meanings of A i t Aβ, Aa, A ?0, A ?6, xß, A ?9, A20, A26, A - ,,, and A32 is alkyl with 1 to 4 carbon atoms, in particular methyl . A preferred meaning of A3i is dodecyl.
A preferred meaning of R is -COO- (alkyl having 10 to 18 carbon atoms), in particular ~ COO-C13H27. Examples of alkoxy having 1 to 12 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy and dodecyloxy. Alkoxy with 1 to 4 carbon atoms in particular methoxy is preferred. Examples of alkenyl having up to 20 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. The carbon atom in position l is preferably saturated. Examples of cycloalkyl with 5 to 12 carbon atoms are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl, cycloalkyl with 5 to 8 carbon atoms, in particular cyclohexyl is preferred. Cycloalkyl with 5 to 12 carbon atoms substituted with alkyl having 1 to 4 carbon atoms, for example, is methylcyclohexyl or dimethylcyclohexyl. Examples of alkylene having up to 10 carbon atoms are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene. An example of cycloalkylene with 5 to 7 carbon atoms is cyclohexylene.
An example of alkylene with 1 to 4 carbon atoms di (cycloalkylene with 5 to 7 carbon atoms) is cyclohexylene-ethylene-cyclohexylene. When the radicals AX1, Ai2 and Ai3 together with the nitrogen atom to which they connect, form a heterocyclic ring of 5 to 10 members, this ring for example is A 6-membered heterocyclic ring is preferred. When the radicals AX4 and AX5, together with the nitrogen atom to which they connect, form a 5- to 10-membered heterocyclic ring, this ring, for example, is 1-pyrrolidyl, piperidino, morpholino, 1-piperazinyl, 4-methyl-1- piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl-4, 5, 5, 7-tetramethyl-1-homopiperazinyl. Morpholino is particularly preferred. An example of an alkyntethiyl having 1 to 4 carbon atoms is 1,2,3,4-butantetrail. ba is preferably a number from 2 to 25. b3 is preferably a number from 2 to 25, especially 2 to 20 or 2 to 10. b4 ', b4"and b4"' is preferably a number from 2 to 4, in particular 2 or 3. b5 is preferably a number from 1 to 25, especially 20 or 1 to 10. b6 is preferably a number from 2 to 25, in particular 2 to 20 or 2 to 10. Ai, A ,, Aio, A18, Aao, A26, A29 and A32 are preferably hydrogen or alkyl having 1 to 4 carbon atoms, in particular hydrogen or methyl. Preferred examples of a compound of the formula (la) are: H- N and ~ > -_ O- C ?? (C Z) S? C? O _ (N - H (ta-3) H3C CH, H3C CH_ Preferred examples of a compound of the formula (Ib) are: H, C - CH - CH CH, (ib-1) R R R R where the radicals R are -C00-C? 3H27 and in a ratio of 1.7: 2.3. H2C - CH - CH - CH2 (Ib-2) R R R R wherein the radicals R are -C00-Cx3H27 and in a ratio of 1.7: 2.3. A preferred example of a compound of the formula (II) is: HN - (CH 2) 3 - N - (CH 2) 2 - N - (CH 2) 3 - NH (II-1) R R R R with R which is the group Preferred examples of a compound of the formula (VI) are: (VI-1) with b2 which is a number from 2 to 25. A preferred example of a compound of the formula (VII) is: with b »which is a number from 2 to 25. A preferred example of a compound of the formula (VIII-a) is HaN - (CH2) 3 -NH- (CH2) 2 -NH- (CH2) 3 -NH2 and A preferred example of a compound of the formula (VIII-b) is Preferred examples of a compound of the formula (IX) are: OX-1) (IX-2) on s that is a number from l to 20.
A preferred example of a compound of the formula (X) is: A preferred compound of the formula (XII) is: with b6 being a number from 2 to 20. A preferred compound of the formula (XIII) is; A preferred compound of the formula (XIV) is: Preferred examples of a compound of the formula (XV) are: The compounds of the formulas (la), (Ib), (II), (V), (VI), (VII), (IX), (X), (XII), (XIII), (XIV) and ( XV) as well as the reaction product described under f) are known (in some cases commercially available) and can be prepared by known methods as described, for example in the US patents Nos. US-A-3 640,928, US-A-4 108 829, US-A-3 925 376, US-A-4 086 204, US-A-4 331 586, US-A-5 051 458, US. -A-4 529 760, US-A-5 182 390, US-A-4 233 412, GB-A-2 269 819, US-A-4 356 307, US-A-4408051 and US-A-4477615 (Chemical Abstracts-CAS No. 136 504-96-6). Preferred examples of a compound of the formula (la) are TínuvinMK 144, TinuvinKR 292, Tinuvin ™ 770, Mark "1 * LA 52, MarkMB LA 57 and bie [l, 2,2,6,6-pentamethylpiperidin-4-yl] n-butylmalonic acid ester, preferred examples of a compound of formula (Ib) with Mark "R LA 62 and MarkMR LA 67; a preferred example of a composition of the formula (II) ee ChimassorbME 199; Preferred examples of a compound of the formula (VI) are Chimassorb "* 944, Cyaeorb * 01 UV 3346 and Dastib1 ** 1082, preferred examples of a compound of the formula (VII) are Uvasil ™ 299 and Uvasil" 11 125; Preferred examples of a compound of the formula (IX) are Mark "* LA 63 and Mark" 11 LA 68; A preferred example of a compound of the formula (XII) ee Tinuvin "1 * 622, a preferred example of a compound of the formula (XIII) is Sanduvor1 * 1 * PR-31, a preferred example of a compound of the formula XIV) is Sanduvor "1 * 3056; a preferred example of a compound of the formula (XV) is Sanduvor ™ * 3050 and a preferred example of the reaction product described under f) is Uvasorb1 ** HA88. The reaction product described under f) can be prepared analogously to process and known, for example by reacting a polyamine of the formula (VIII-a) with cyanuric chloride, in a molar ratio from 1: 2 to 1: 4 in the presence of anhydrous lithium carbonate, eodium carbonate, or potassium carbonate in an organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-alkyl alcohol, at a temperature from -20 aC to + 10 ° C, preferably from -10 ° C to + 10 ° C, in particular from 0 ° to + 10 ° C, from 2 to 8 hours, followed by reaction of the resulting product with a 2,2,6,6-tetramethyl-4-piperidylamine of the formula (VlII-b). The molar ratio between 2,2,6,6-tetramethyl-4-piperidylamine and polyamine of the formula (VlII-a) for example is from 4: 1 to 8: 1. The amount of 2,2,6,6-tetramethyl-4-piperidylamine may be added in one portion or in more than one portion at intervals of a few hours. The ratio of polyamine of the formula (VIII-): chloridecyanuric: 2, 2, 6, 6-tetramethyl-4-piperidylamine of the formula (VlII-b), is preferably from 1: 3: 5 to 1: 3: 6 . The following example indicates a way of preparing a preferred compound of the reaction product described under f). Example: 23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol) of N, N'-bie [3-aminopropyl] -ethylendia ina and 18 g (0.13 mol) of anhydrous potassium carbonate are reacted at 5 ° C for 3 hours with stirring in 250 ml of 1,2-dichloroethane. The mixture is heated at room temperature for a further 4 hours. 27.2 g (0.128 mol) of N- (2, 2, 6, 6-tetramethyl-4-piperidyl) utylamine are added, and the resulting mixture is heated to 60 ° C for 2 hours.Additional 18 g (0.13 mol) of Anhydrous potassium carbonate is added and the mixture is heated at 60 ° C for a further 6 hours.The solvent is removed by distillation with slight vacuum (200 mbar) and replaced by xylene 18.2 g (0.085 mol) of N- (2, 2,6,6-tetramethyl-4-piperidyl) butylamine and 5.2 g (0.13 mol) of ground sodium hydroxide are added, the mixture is refluxed for 2 hours and for 12 more hours, the water formed during the reaction is removed by azeotropic distillation The mixture is filtered, the solution is washed with water and dried over Na 2 SO.The solvent is evaporated and the residue is dried at 120-130 ° C under vacuum (0.1 mbar) The desired compound is obtained as a colorless resin In general, the reaction product described under f) may be represented, for example, by a compound of the formula VIII-1, VIII-2 or VIII-3. e a mixture of these three compounds (Vfll-2) (Vill-3) A preferred eignificate of the formula (VIII-1) A preferred eignificate of the formula (VIII-2) is A preferred meaning of the formula (V1II-3) ee In the above formulas (VIII-1) to (VIII-3), b4 is preferably 1 to 20. The meanings of the terminal groups that saturate the free valencies in the compounds of the formulas (VI), (VII), ( VIII-1), (VIII-2) and (VIII-3), (IX) and (XII) depend on the processes used for their preparation. The end groups can also be modified after the preparation of the compounds. In the compounds of the formula (VI), the end group linked to the tpazine radical may, for example, be chlorine or a group - M - AM - N - H and the extreme group linked to the diamino group can for example be hydrogen or a group "16 14 It may be convenient to replace the chlorine connected to the triazine for example by -OH or an amino group. Suitable amino groups are typically eon: pyrrolidin-1-yl, morpholino, -NH2, ~ N (alkyl with 1 to 8 carbon atoms) 2 and -NY '(alkyl with 1 to 8 carbon atoms), where Y' is hydrogen or a group of the formula (IV). In the compounds of the formula (VII), the terminal group linked to the eilium atom can for example be (A16) 3-Si-0-, and the terminal group linked to the oxygen atom can for example eer -Si (A? 6) 3. The compounds of the formula (VII) can also be in the form of cyclic compounds, and t is a number from 3 to 10, ie the free valencies iluetradae in the structural formula then form a direct bond. In the compounds of formulas (VIII-1), (VIII-2) and (VIII-3), the terminal group linked to the triazine radical, for example, is Cl or a group and the terminal group linked to the amino radical, for example is hydrogen or a group In the compounds of the formula (IX), the radical group linked to the radical > C = 0 can for example be -OH, alkoxy with 1 to 4 carbon atoms or and the end group linked to the oxygen atom for example can be hydrogen or In the compounds of the formula (XII), the end group linked to the -O-, may for example be hydrogen or a group -C0-A2β-C00-Y ", with Y" which is hydrogen or alkyl with 1 to 4 atoms. of carbon and the extreme group linked to the diacyl radical can for example be -o ~ Y "or a group According to a preferred embodiment, Ai is hydrogen or alkyl having 1 to 4 carbon atoms, if i is 2, A2 is alkylene with 2 to 8 carbon atoms or a group of the formula and if i is 4, A2 is 1, 2, 3, 4-butantetraílo, the radicals R independently of each other are -C00-C? 3Ha or a group A3 and A7 independently of each other are hydrogen or alkyl having 1 to 4 carbon atoms, ,, As and As independently of each other are alkylene with 2 to 3 carbon atoms, Ti, T2, T3, T4, TB, Tß, T7 and T8 independently of each other are a group of the formula (III), wherein A8 is hydrogen, alkyl having 1 to 4 carbon atoms or a group of the formula (IV), A11, A13, Ai4 and AiS independently of each other are hydrogen , alkyl having 1 to 8 carbon atoms, cyclohexyl or a group of the formula (IV), Aiz is alkylene with 2 to 10 carbon atoms, or An and Ais, together with the nitrogen atom to which they are bound form morpholino, b2 is a number from 2 to 25, Ai6 is alkyl with 1 to 4 carbon atoms, cycloalkyl or phenyl, A? 7 is alkylene with 3 to 8 carbon atoms, b3 is a number of 2 to 25, b?, b4. and bt.r independently of each other are a number of 2 to 3, Ai, is hydrogen or alkyl with 1 to 4 carbon atoms, A2 ?, A23, A2 «and A25 independently are alkylene with 1 to 4 carbon atoms, A22 is a direct bond, bs is a number from 1 to 20, A28 is alkylene with 2 to 8 carbon atoms, b6 is a number from 2 to 25, A3D is alkoxy with 1 to 4 carbon atoms, A3 is C? 2H25 and A34 is alkyi with 12 to 14 carbon atoms. According to a further preferred embodiment, one of the two different compounds containing a residue of the formula (A) is the compound of the formula (la-l), (Ia-2), (Ia-3), (la-4), (Ia-5), (II-l), (VI-1), (XII-1) or (XIII-1). The two different compounds containing a residue of the formula (A), are preferably chosen from the group that connects the compounds of the formulas (Ia-1), (Ia-2), (Ia-3), (Ia- 4), (Ia-5), (Ia-6), (Ib-1), (lb-2), (II-1), (VI-1), (VI-2), (VI-3), (VII-1), (VIII-1), (IX-1), (IX-2), (XII-1), (XIII-1) and (XIV-1) in particular (Ia-1), (Ia-2), (Ia-3), (Ia-6), (Ib-1), (II-1), (IX-2), (XII-1) (XIII-1) and (XIV-) 1) or the group consisting of the compounds of the formulas (Ia-1), (Ia-2), (Ia-3), (Ia-4), (Ia-5), (11-1), ( VI-1), (XIII) and (XI1I-1). According to a particularly preferred embodiment of this invention, the two different compounds containing a radical of the formula (A) are the compounds of the formulas (II-1) and (VI-1), the compounds of the formulas ( 11-1) and (XII-1), the compounds of the formulas (Ia-1) and (Ia-3), the compounds of the formulas (Ia-2) and (II-1) or the compounds of the formulas (la-3) and (II-l). When the two different compounds contain a residue of the formula (A) are of resinous nature, it is preferred that their particle size be less than 2 mm and more preferably less than 1 mm. This ensures that the compounds are easily incorporated into the powder coating composition in a single pass extruder. Two main methods are currently in use for charging powder paint: corona and triboelectric charge, which are well described in the literature (TA Mieev; "Powder Coatinge: Chemietry and Technology" (Powder Coatings: Chemistry and Technology ), John Iley &Sons, Chichester, 1991, pages 324-344). In the prior art, the powder is bombarded by ions as it passes through a high electric field. This last technique, which is of great importance, uses the phenomenon of frictional loading. In tripo-electric charge, the powder is trapped in a jet of air and sprayed by a conventional annular tube. The air flow velocity should be sufficient to cause tuent flow and in this way ensure good contact between the powder and the tube. The electric charge separation occurs between the surface of the dust particle and the wall of the charging tube. The charge in the tube leaks to the ground and the dust emerges from the highly charged charging tube. There are a number of reasons why tribolelectric charge is used so widely in practice. First, the absence of a high-voltage source is an obvious safety benefit, even though the design of crown-coating guns has advanced to date to virtually eliminate the dangers of a dust explosion. Secondly, the crown guns emit a large amount of free ions, which together with the charged powder, also move towards the work piece. As the powder thickness accumulates in the workpiece, a process known as counterionization begins to occur, where the powder is rejected from the surface and subsequently causes heterogeneity and craters in the cured coating. In a corona-applied powder, the onset of counter-ionization is much earlier, due to the large amount of free ions trapped in the resist. A third reason is that unlike corona charging, there is no high electric field or Faraday cage effect in triboelectric charge, so that dust can be applied more easily to concave object and in recess areas. For all these reasons it is important that powder paints are suitable for triboelectric application. There is also a practical aspect: a manufacturer of powder paint, often does not know what equipment can apply who applies the coating and surely do not want to have a double range of powders, one suitable for corona and the other suitable for triboeléctrica application. In powder coatings, it is important that regardless of whether a triboelectric charging technique or corona is employed, the powder paint particles are highly charged. A high electrical charge in the powder ensures good efficiency of the coating process; that is, proportionally more dust ends up in the work piece and less of the excess spray will have to be recycled. In addition, a very low dust load causes deficiency of dust adhesion to the work piece. If the dust load is very high, however dust particles will strongly repel each other and the dust packing in the workpiece will be loose. Also, it will occur against ionization in a previous stage as the coating thickness accumulates. The net effect of both procedures is a loss in the quality of the coating surface. In practice, therefore, there is an optimum charge / mass ratio for triboelectric application, which depends on the factor such as the specific gravity of the powder, the surface regularity and the average particle size, etc. The measurement of the efficiency of the triboelectric charging process is basically simple, although it is often misunderstood. Starting from the basic relation between electric current (I), charge (Q) and time (t): I = Q / t the following relationship can be derived, taking into account the dust mass (m): I = (Q / m) x (m / t) From this equation it can be seen that it is bad practice to take the triboelectric current as a measure of the efficiency of the triboelectric charging process, since this will be proportional to the powder flow rate (m / t), provided that conditions of turbulent flow and the limiting condition are met where the collision between the dust particles rather than the tube does not occur in a large proportion. A better indicator of the efficiency of the charging process is therefore the charge / mass ratio (Q / m). This can already be calculated from the triboelectric current when the powder flow expense is known or measured directly. An instrument for this purpose is described in the document prepared by Kleber and Lang in the 9th. International Electroethics Conference, York, 2-5 April 1995 (Inet. Phye. Conf. Ser. No. 143, pages 201-204). For the reasons set forth above, a preferred embodiment of this invention is a powder coating composition containing 1) an organic film-forming binder, and 2) at least two different compounds containing a residue of the formula (A) as electron donors, characterized in that the powder coating composition has a charge / mass ratio of at least 200 μC / kg and preferably does not exceed 10 000 μC / kg. Preferred ranges are 200-2000 μC / kg, 400-2000 μC / kg and 600 -1000 μC / kg.
For a powder release having a specific gravity of 1.3 to 3.0 g / cm 3, a preferred embodiment of this invention is a powder coating composition having a charge / mass ratio of at least 200 μC / kg and not exceeding 5 000 μC / kg, in particular 2000 μC / kg; more preferred is a charge / maea ratio in the range 400-2000 μC / kg and in particular the range is 600 to 2000 μC / kg, for example 600-1500 μC / kg. For a powder coating having a specific gravity of 0.8 to 1.3 g / cm 3, a preferred embodiment of this invention is a powder coating composition having a charge / mass ratio of at least 400 μC / kg and not exceeding 10 000 μC / kg, a charge / mass ratio in the range 400-2000 μC / kg is more preferred. This invention also relates to a method for charging the powder coating composition as defined herein, which comprises charging the powder coating composition with a charge / mass ratio of at least 200 μC / kg in a tribocharged pellet. This invention also relates to a method for triboelectrically applying a powder coating composition as defined herein to a metal sub-layer.
Also a preferred embodiment of this invention is the mixing of a mixture comprising at least two different compounds containing a residue of the formula (A), as electron donors for a powder coating composition comprising an organic film-forming binder. . This invention furthermore relates to a powdery release composition containing 1) an organic film-forming binder, and 2) at least two different compounds, selected from the group consisting of the compounds of the formulas (Ia-4), (Ib-1), (Ib-2), (11-1), (VI-1), (VI-2), (VI-3), (V1I-1), (VIII-1), (IX-1), (IX-2) and (XII-1), as defined above, in particular the compueetoe of the formulas (Ia-4), (Ib -1), (II-1), (IX-2) and (XII-1), for example (II-1) and (XII-1). In the past, the triboelectric charge of powder paints was often inefficient or disengaged and it was found useful to assist the triboelectric charge of the powder by adding a poetry crown to the end of the pietola, which can be turned on, off or adjusted accordingly. with the need. Although the triboelectric charge that is achieved by the additives according to this invention (component (2)) is fully adequate to ensure a good tribocharge, powders made as described herein, can of course also be applied using this type of equipment. An additional development of triboelectric dust release is described in O-A-96/15 199 where particles of powder paint are frictionally charged by contact with magnetic or non-magnetic carrier particles and are subsequently transferred to a substrate. For said sevenmae, the powder coating compositions according to this invention are excellently suitable. With the purpose of the working capacity of this efficient invention, the load occurs by friction and does not depend on the geometry or forms the contact partner. For example, triboelectric pietolae are also known where the loading tube is wound in a spiral or ending in a number of individually steerable "fingers": also for these sevenmas, mixtures of the compounds containing a residue of the formula (A) (= component (2)) work well. The equipment used to charge the powder coating compositions of this invention can also be connected to a powder metering device, an example of which is described in EP-A-678 466. Similarly, the working capacity of this invention is not It is reetringe to any particular contact material in the loading process. Convenient contact media materials, include for example polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyethylene, polypropylene, fluorinated and non-fluorinated ethylene / propylene copolymer, polymethyl methacrylate and polyetherane and in particular polytetrafluoroethylene (PTFE). The mixing of the 2,2,6,6-tetramethylpiperidine derivatives (component (2)) does not re- strict to any particular powder reagent chemistry. The effect of the 2, 2, 6,6-tetramethylpiperidine derivative on the charge / mass ratio is approximately proportional to the amount of the derivative employed, so that in principle, any powder coating composition can be given a tribocharge when adding an appropriate amount. The definition of "powder coatings" is understood to be that which is described in the Ullman's Encyclopedia of Industrial Chemistry, fifth edition, fully revised, volume 18, p. 438 to 444 (1881) in Section 3.4. The powder coatings are in particular thermoplastic or polymer and interlatable for baking, which are applied in powder form to predominantly metallic substrates. The manner in which the powder comes into contact with the workpiece to be coated is in accordance with this invention preferably sprayed with electrostatic powder. The applied particles that are adhered by Coulomb forces in the work piece melt in an oven and cure. The baking temperatures usually employed are 140 ° C to 260 ° C, in particular 140 'to 220 ° C, and depend mainly on the chemistry of the powder coating formulations and the design of the oven. they are typically in the range from several minutes to half an hour.In the case of UV curable systems, after application to the substrate, the powder coating composition according to this invention, first melts or heats, rapidly using infrared radiation, at a temperature of 50 ™ C to 180"c. Subsequently, the coating is cured with UV light, preferably while it is still hot. A further preferred embodiment of this invention is a cured powder coating, made from a powder coating composition as described above. Preferred substrates are metal substrates such as for example those of iron, steel, copper, zinc, tin, magnesium, titanium or aluminum and their alloys. Steel and aluminum and are alloyed with particular interest. Preferred powder coating compositions are those in which the organic film-forming binder is a polyester or polyacrylate reein together with an entanglement agent or an epoxy resin, or combinations of these resins. Polyesters in general are hydroxy-functional or carboxy-functional and are commonly prepared by condensation of dioids and dicarboxylic acids. By adding polyole and / or polyacid, branched polyetherenes are obtained which, upon baking in the presence of entanglement agent, give rise to network structures which give the coating the desired physical properties such as scratch resistance, impact resistance and resistance. flexural Instead of polyfunctional acid it is also possible to use anhydride or acid chlorides, for example maleic anhydride, itaconic anhydride, phthalic anhydride, terephthalic anhydride, hexahydroterephthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, succinic anhydride, etc. It is also possible to use simple esters, for example dimethylene terephthalate, in which case the transesterification polymerization is carried out with the elimination of volatile alcohol. Likewise, the preparation is practicable when combining traneesterification and condensation. In addition, polyesterers can be prepared by polycondensation of hydroxycarboxylic acids, for example 12-hydroxyethearic acid and hydroxypivalic acid., or of the corresponding lactones, for example epsilon-caprolactone. Examples of carboxylic acid and polyacid include terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, 1,12-dodecandioic acid, pyromellitic acid, 3,6-dichlorophthalic acid, euccinic acid, 1,3-cyclohexanedicarboxylic acid, and acid 1,4-cyclohexanedicarboxylic acid. Examples of diole and polyols include ethylene glycol, propylene glycol, glycerol, hxantriol, haxan-2,5-diol, hexane-1, 6-diol, pentaerythritol, sorbitol, neopentyl glycol, trimeti loletane, trimethylolpropane, tris-1,4-cyclohexanedimethanol. , trimemethylene diol, 2, 2-diethyl-1, 3-propanediol, 2-methyl-2-butyl-l, 3-propanediol, diol ester 204 (hydroxypivalic acid ester and neopentyl glycol), hydrogenated bis-phenol A, bisphenol A, hydroxypivalic acid, hydroxypivalate esters, 2-butyl-2-ethyl-l, 3-propanediol, 1,4-butanediol, 2-buten-l, 4-diol, 2-butin-l, 4-diol or 2-methyl-1 , 3-propanediol. Suitable crosslinking agents for carboxy-functional polyesterers are epoxy compounds such as, for example, epoxy novolak resins, diglycidyl ethers of bisphenol A, hydrogenated bisphenol A and bisphenol A modified by reaction with, for example, aliphatic dicarboxylic acids. Also suitable are reactive epoxy compounds such as triglycidyltriazolidine-3,5-dione, glycidyl esters of polyacids, for example diglycidyl terephthalate and diglycidyl hexahydroterephthalate, hydantoin epoxides (US-A-4, 402 983) and, most particularly, triglycidyl isocyanurate, epoxidized unsaturated fatty acid esters of glycerol (UranoxMB DSM) and Araldit "* PT910 (" "Ciba Specialty Chemicals) Other entanglement agents for carboxy-functional polyether ether are beta-hydroxyalkylamides (US-A-4076 917), for example the derivative of predominantly tetrafunctional beta-hydroxyalkylamide of adipic acid (Primid1 ™ * XL552 and QM1260 from "EMS Chemie") Other that have proven to be suitable include melamine, benzoguanimine and glycoluril derivatives, which are alkylated with low molecular weight alcohols. etiimetoxiglícolurilo (PowderlinkMB 1174 of "" American Cyanamid) Other known entanglement agents are bis- and tris-oxazo Lidins, for example 1,4-bieoxazolidinobenzene. A recent development comprises carboxy-functional polyesters containing chemically epoxy groups and are also capable of interweaving with themselves (Molhoek et al., 22nd Fatipec Congress, 15.-19.5.95, Budapest, Vol. 1, 119-132). . In all systems where an expoxy group or a glycidyl radical reacts with a carboxyl group or an anhydride in an entanglement reaction, catalysts may be employed. Examples are amine or metal compote, for example aluminum acetylacetonate or ethane octoate. As a sealant for hydroxy-functional polyesters, the polyisocyanate crosslinkers are of particular importance. In order to avoid premature entanglement due to the high reactivity of isocyanates, and in order to obtain good leveling of the fused powder, the polyisocyanates are blocked (internally as an uretdione or as an adduct with a blocking agent). The most frequently used blocking agents used are epsilon-caprolactam, methyl ethyl ketoxime or butanone oxime. Other suitable blocking agents for isocyanates are prescribed in the publication of G.B. Guiee, G.N. Freeland and G.C. Smith; J. Applied Polymer Science, 2, 353 (1979) and M. Bock and H.-U. Maier-Weethuee in "Progress in Product Development for Powder Coating Technology" (Advance in Product Development for Powder Coating Technology) XIX International Conference on Organic Coating, Science and Technology, Atenae, July 12-16, 1993.
Examples of block or blockless polyisocyanates include 2-methylpentane-1, 5-diisocyanate, 2-ethylbutane-1, 4-diieocyanate, 3 (4) -ieocyanatomethyl-1-methylcyclohexyl isocyanate, 3-isocyanatomethyl-3, 5, 5- trimethylcyclohexane diisocyanate, tris (isocyanatomethy) benzene, 4,4-diiocyanatodicyclohexylmethane, 1,4-bicyclo (ethyl) cyclohexane, m-tetramethylxylene diieocyanate, p-tetramethylxylene diieocyanate and, in particular, iodophorone diiocyanate. For the reaction of the polyol with the polyethocyanate, a metal catalyst, for example zinc octanoate, titanium octanoate, dibutyltin oxide or dibutyl tin dilaurate, is added to the polyisocyanate formulation. Other crosslinking agents suitable for hydroxy-functional polyesterers are anhydrides, for example trifellitic anhydride and their reaction products with diols and diamines. Adicionaies examples of these entanglement agents are described by T.A. Misev in "Powder Coatings: Chemistry and Technology" (Powder Coatings: Chemistry and Technology), John Wiley & Sons, Chichester, 1991, pages. 123 and 124. Preferred entanglement agents for polyesters are an epoxy resin, triglycidylisocyanurate, giicoluril, hydroxyalkylamide, uretdione and block polyisocyanate.
Polyacrylates. which usually have hydroxy, carboxy or glycidyl functionality are also used as binders for powder coating. They are prepared by the usual methods, predominantly from monomers such as ethene and alkyl with 1 to 8 carbon atoms, linear or branched, of acrylic acid or methacrylic acid. Other ethylenically unsaturated compounds, for example divinylbenzene, acrylamide, methacrylamide, butoxymethylacrylamide, acrylonitrile, butadiene, etc., can also be added and copolymerized. The hydroxy functionality is provided by the copolymerization of hydroxy functional monomers such as for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate. For carboxy functionality, ethylenically unsaturated acids and anhydrides, for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, acrylic anhydride or methacrylic anhydride are used (US-A-3 836 604). The glycidyl functionality is provided as illustrated in EP-A-0 256 369 and US-A-3 876 578, by the copolymerization of monomers such as glycidyl acrylate and glycidyl methacrylate. As entanglement agents for polyacrylates with hydroxy or carboxy functionality it is in principle possible to use the same compounds as already described for polyesters with hydroxy or carboxy functionality. Additional suitable entanglement agents are the epoxy compounds of US-A-0 045 040. Preferred entanglement agents are an epoxy resin, triglycidyl isocyanurate, glycolurium, hydroxyalkylamide, uretdione and block polyisocyanate. Suitable entanglement agents for polyacrylates with glycidyl functionality are dicarboxylic acids such as for example cebacic acid and 1,12-dodecandioic acid and anhydrides, for example bie-trimellitic anhydride and compotetoe described in US-A-3 880 946. They are also known in addition, self-linking polyacrylates of DE-A-3 310 545. It has been found that the mixture of the compounds containing a residue of the formula (A) (= component (2)) is particularly suitable for improving the triboelectric charging capacity of the polyacrylates. Epoxy resins for powder coatings are primarily any novolac-epoxy resins or in particular those based on aromatic polyols, especially bisphenols such as bisphenol A. Bisphenol-epoxy modified resins of JP-A-58 187 464 (1982) are also known. ). Epoxy reeins are used in combination with entanglement agents of the solid aliphatic amines classes, solid aromatic amines, adducts of amines, phenolic resins, polyacids and the carboxy-functional polyesters already described. Hardeners (curing agents) that merit special attention are the dicyandias which are frequently used together with a catalyst such as for example Lewis acids, boron trifluoride amine complexes, metal complexes, tertiary or quaternary amines and imidazoline derivatives such as -methylimidazoline. Powder coating compositions typically use an approximately stoichiometric ratio of resin to crosslinking agent. Variations of the stoichiometric ratio of more than 30%, almost always result in a deterioration in the physical properties of the cured coating, such as flexibility, impact resistance, adhesion, weathering or weather resistance and resistance to eoliness, etc. Also of interest are film-forming binders with thermophatic properties, examples being polyethylene, polypropylene, polyamides, polyvinyl chloride, polyvinylidene dichloride or polyvinylidene difluoride. In addition, powder coatings comprising ethylenically unsaturated components and can be cured with photoinitiators are also known.
Preference is given to powder coating compositions wherein the organic film-forming binder (component (1)) is an ethically unsaturated component that can be cured in the presence of a photoinitiator with light, especially ultraviolet light. Examples of appropriate light sources are mercury lamps with medium pressure or high pressure. The powder coating compositions according to this invention may further comprise conventional additives such as pigments, colorants, fillers, flow aids, degassing agents, optical brighteners, adhesion promoters, photoinitiators, anti-corrosion agents, antioxidants, UV amberblows, stabilizers. of light and so on. The pigments are, for example, titanium dioxide, iron oxide, carbon black, aluminum bronze or phthalocyanine blue. Examples of dyes are polyester dyes and solvent dyes. Examples of fillers are talc, alumina, aluminum silicate, barite, lithopone, calcium carbonate, mica or silica. Examples of flow auxiliaries are epoxy fatty acids, abietyal alcohol, polylauryl methacrylate, polylauryl acrylate, polydimethylethyloxane-polyalkylene oxide block copolymers or in particular low molecular weight copolymers and alkyl esters of 1 to 8 carbon atoms, acrylate or alkyl. methacrylate esters. Examples of degassing agents are fatty acid amides as described in EP-A-0 471 409, e-caprolactam, methyl isophthalate and dimethyl isophthalate (EP-A-0 284 996) and especially benzoin. An example of a particularly convenient optical brightener is Uvitex ^ OB ("" Ciba Specialty Chemicals). Adhesion promoters are based for example on modified siianes, titanates or zirconates. Suitable photoinitiators are those based on benzophenones, phenyl glyoxalates, bia- or mono-acyl-phenoxy, a-hydroxy-ketone or benzyl dimethyl-ketals and especially their combinations. Examples of anticorrosive agents are anti-corrosive pigments such as phosphate-or borate-containing pigments or metal oxide pigments, or other organic or inorganic corrode inhibitors, for example salts of nitroisophthalic acid, phosphoric ethers, technical grade amines or substituted benzotriazoles. Examples of antioxidants are: 1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4- Ethyl enol, 2,6-di-tert-butyl-4-n-butyl-1-phenol, 2,6-di-tert-butyl-4-isobutylphenol, 6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) ) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 4,6-tri-cyclohexyphenol, 2,6-di-tert-butyl-4-methoxy-aralphenol, nonylphenols which are linear or branched in the chains secondary, for example 2,6-di-nonyl-4-methyl-phenol, 2,4-dimethyl-6- (1-ethylundec-1-yl) phenol, 2, 4-dimethyl-6 ~ (l ' -methyl-heptadec-1-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof. 2. Alkyltiomethylphertoles, for example 2,4-dioctiitiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol. 3. Hydroquinones and alkylated hydroquinones. for example 2, 6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-buty-hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecylphenol, 2, 6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-1-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy phenyl etherate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate. 4. Tocopherols, for example α-tocopherol, β-tocopherol, y-tocopherol, α-tocopherol and their mixtures (Vitamin E). 5- Hydroxylated thiodiphenyl ethers for example 2,2'-thiobis (6-tert-butyl-4-methylphenol =, 2, 2'-thiobis (4-octylphenol), 4,4'-thiobis (6) tert-butyl -3-methylphenol), 4,4'-thiobie (6-tert-buty-2-methylphenol), 4,4'-thiobis (3,6-di-sec ~ a ilf enol), 4,4 '-both - (2,6-dimethyl-4-hydroxy-enyl) -dulphur. 6. Alquilidenbisf enols, for example 2,2'-methylenebis- (6-tert-buty-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-] met i 1-6- (- ethylcyclohexyl) phenol J, 2,2 '-methylenebis (4-methyl 1-6-cyclohexyl-f-enol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidebisbis (4,6-di-tert-butylphenol), 2,2'-ethylidebisbis (6-tert-butyl-4) -isobutyl enol), 2, 2 '-methylenebis [6- (a-methylbenzyl) -4-nonylifen], 2,2'-methylenebis [6- (, -dimethylbenzyl) -4-nonylphenol], 4.4 '-methienbis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2) -methylphenii) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1, 3-tris (5-tert-buty-4-hydroxy-2) methylmethyl) butane, 1,1-bie (5-tert-butyl-4-hydroxy-2-methyl-phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol, bi [3, 3-bi (3'-ester -butyl-4 '-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene , bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl-1-terephthalate, 1,1-bis (3,5-dimethyl) -2-hydroxy-phenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxy-enyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) ) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane. 7. O-, N- and S-benzyl compounds, for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate , tridecyl-4-hydroxy-3, 5-di-tert-butylbenzylmercapto-acetate, tris (3, -di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) itioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfur, isooctyl-, -di-tert-butyl-4-hydroxybenzylmercaptoacetate. 8. Hydroxybenzyl malonates. for example dioctadecyl-2, 2-bis- (3, 5-di-tert-butyl-2-hydroxybenzyl) -malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methyl-benzyl) ) malonate, di-dodecyl mercaptoethyl-2, 2-bie- (3,5-di-tert-i-l-4-hydroxybenzyl) alonate, bi s [4- (l, 1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3, 5-di-tert -but i 1-4-hydroxybenzii) malonate. 9- Aromatic hydroxybenzyl compounds, for example 1,3,5-tris- (3, 5-di-tert-butyl-4-hydroxybenzii) -2,4,6-trimethylbenzene, 1,4-bie (3, - di-tert -but i 1-4-hydroxybenzyl) -2, 3, 5, 6-tetramethylbenzene, 2,4,6-trie (3,5-di-tert-butyl-4-hydroxybenzii) phenol. 10. Compueetoe triazina. for example 2,4-bie (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyimercapto-4,6-bie (3,5 -di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -l, 3 , 5-triazine, 2,4,6-tris (3,5-di-t-r-butyl-4-hydroxyphenoxy) -l, 2,3-triazine, 1,3, 5-tris- (3, 5 -di-tert-buty-4-hydroxybenzyl) -isocyanurate, 1, 3, 5-tris (4-tert-buty-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3, 5-di-tert-butyl-4-hydroxy-phenylethyl) -1,3,5-triazine, 1,3,5-trie (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1, 3, 5-triazine, 1,3,5-trie (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate. 11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylfoephonate, dioctadecyl-3,5-di-ter- butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the 3,5-di-tert-butyl-4-hydroxybenzyl-phophonic acid monoethyl ester. 12. Acylaminophenols. for example 4-hydroxylauranylide, 4-hydroxyetheranylanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate. 13. Esters of acid - (3,5-di-tert-butyl-4-hydroxyphenyl-1-pro-ionic) with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanoi, octadecanol, 1,6- hexandiol, 1,9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis (idroxyethyl) oxamide, -thiaundecanol, 3-thiapentadecanol, triraethylhexandial, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane 14. Esters of β-5-tert-butyl-4-hydroxy acid 3- Ethylphenyl propionic with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thioethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-benzene (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexandiol, trimethylolpr Opane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane. 15. B- (3, 5-dicyclohexyl-4-hydroxyphenyl) ropionic acid esters, with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycoi, thiodiethylene glycol, diethylene glycol, tricyethylene glycol, pentaerythritol, tris- (hydroxyethyl) -ieocyanurate, N, N'-bis (idroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, tri ethylhexandiol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6,7-trioxabicyclo [2.2.2] octane 16. Steree of 3,5-dj-tert-butyl-4-hydroxyphenyl acetic acid, with monohydric alcohol or polyhydric for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tethylene glycol, pentaerythritol, tris ( hydroxyethyl) -isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanoi, 3-thiapentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-tri oxabicyclo [2.2.2] octane. 17. Amides dg ñ- (3,5-di-tert-butyl-4-hydroxyphenyl) ropionic acid. for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) trimethylene diamine, N, N'-bis (3, -di-tert-buty1-4-hydroxyphenyl-propionyl) hydrazine. Examples of UV absorbent and other conventional additives are: I • 2- (2'-Hydroxyphenyl) benzotriazoles, for example 2- (-hydroxy-5'-phenylphenyl) -benzotriazole, 2- (3 ', 5'-di- tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) ) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- methylphenyl) -5-chloro-benzotriazole, 2- (3 '-sec-butii-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) enzotriazole, 2- (3', 5'-bis- (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, mixture of 2 - (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy ) -carboniletii] -2 '-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethi) phenyl) -5-chloro-benzotriaz ol, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy) 5'-methylphenyl) benzotriazole y2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (l, l, 3.3 -tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; wherein R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.
II- 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 2 ', 4' -trihydroxy derivatives and 2'-hydroxy-2-derivative , 4 '-dímethoxy. III. Eetßree of substituted benzoic acid? unsubstituted, such as for example 4-tert-butyl phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-ter -butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxy-benzoate, octadecyl 3,5-di-tert-butyl-4-hydroxy-benzoate, 2-methyl-4,6-di -tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate. IV. Acrylates. for example ethyl a-cyano-ß, ß-diphenylacrylate, isooctyl a-cyano-ß, ß-difenii-acrylate, methyl a-carbometoxicinamata, methyl a-cyano-ß-methyl-p-methoxy-cinnamate, butyl a-cyano -β-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylinine. V. Nickel Compounds, for example 2, 2'-thio-bis [4- (1, 1,3,3-tetramethyl-butyl) phenol] nickel complexes, such as the 1: 1 or 1: 2 complex , with or without additional binders such as n-butylane, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithio-carbamate, nickel salts of the monoalkyl esters, for example methyl or ethyl ester, of 4-hydroxy-3,5- di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, for example of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of l-phenyII-4-lauroyl-5-hydroxypyrazole, with or without additional ligands. SAW. Qx mi aS For example 4,4-dioctyloxyoxamide, 2,2-diethyloxyanilide, 2,2'-dioctyloxy-5,5"-di-tert-butoxyanilide, 2,2 -didodecyloxy-5,5-di-tert-butoxyanilide , 2-ethoxy-2-ethyoxyaniide, N, N-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide and eu mixture with 2-ethoxy-2'-ethyl-5, 4-di-tert-butoxyanilide and mixtures of ortho- and para-methoxy-unsubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides VII-2-f 2-Hydroxyphosphile 1-1.3.5-triazines f for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,5,5-triazine, 2- (2-hydroxy-4-octyloxyphenii) -3,6-bis (2,4-dimethylphenyl) - 1, 3, 5-triazine, 2- (, 4-dihydroxyphenyl) -4,6-bie (2,4-dimethylphenyl) -1, 3, 5-triazine, 2,4-bis (2-hydroxy-4-) propyl-oxy nyl) -6- (2,4-dimethylphenyl) -l, 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bie (4-methylphenyl) -l, 3, 5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bie (2,4-dimethylphenyl) -l, 3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4 , 6-bie (2, 4-dim etilfenii) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3 , 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2 - [4 ~ (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [-hydroxy-4-] (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexoxy) phenyl-4, 6 ~ diphenyl-1, 5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4] - (3-butoxy-2-hydroxy-propoxy) phenyl] -l, 3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1, 3,5-triazine . VIII. Metal deactivators, for example N, N'-diphenoxyamide, N-salicylal-N'-ealicyloyl hydrazine,, '-bi (ealicyloyl) hydrazine, N, N'-bis (3, 5-di-ter-butyl 1-4- hydroxyphenylpropionyl) hydrazine, 3-salicylylamino-l, 2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaioyl dihydrazide, sebacoyl biefenilhydrazide, N, N'-diacetyldipoyl dihydrazide, N, N'-bie (ealyloyl) oxalyl dihydrazide , N, N'-bis (salicyloyl) thiopropionyl dihydrazide. IX. Tioeinergietae, for example dilauryl thiodiopropionate or disteary thiodipropionate. X. Peroxide scavengers, for example esters of ß-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecyl mercapto) propionate. The two different compounds containing a residue of the formula (A), together in general are present in an amount of 0.1 to 10%, preferably 0.2 to 5%, in particular 0.5 to 3% by weight of the total solids of the powder release composition. The weight ratio of these two compounds for example is 95: 5 at 5:95, 90:10 at 10:90, 80:20 at 20:80, 70:30 at 30:70, 60:40 at 40:60 or 50:50. According to a preferred embodiment of this invention, the powder coating compositions additionally contain a phosphite or a phosphonite, for example in an amount of 0.01 to 10%, preferably 0.02 to 5%, in particular 0.05 to 3% by weight , with respect to the total solids of the powder composition. Examples of phosphites and phosphonites include triphenyl phenytoin, diphenyl alkyl phryphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite , bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) ~ pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl) -6-methylphenyl) penta-erythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) -pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-bylphenyl) 4,4'- biphenylene diphosphonyl, 6-butooctyloxy-, 4,8, 10-tetra-tert-butyl-12H-dibenz [d, g] -l, 3,2-dioxafoefozin, 6-fluoro-2,4,8,10-tetra -tert-butyl-12-methyl-dibenz [d, g] -l, 3, 2-dioxaphosphocino, bis (2,4-di-tert-butyl-6-methyl-phene) methylphosphite or bis (2,4- di-tert-butyl-6-methylphenyl) ethylphophyte The preparation of powder release compositions according to eeta in can be carried out according to usual methods. A good description of the procedures and machinery can be found in T.A. Misev in "Powder Coatinge: Chemietry and Technology" (Powder Revelations: Chemistry and Technology), John Wiley & amp;; Sons, Chichester, 1991, Chapter 5. In general, all components of the powdered release composition are weighed and mixed together in an appropriate mixer. Mixers used for this purpose are drum mixers, cone mixers, double cone mixers, horizontal mixers, for ulators and stirring units such as planetary mixers. Typically, the formulation is processed in a heated extruder at temperatures typically in the range of 70-120"C, preferably 70-1" c, to obtain a melt of maximum homogeneity. Apparatus suitable for this include single spindle kneaders, double spindle kneaders and planetary extruders. The addition is made in most cases by a screw conveyor, a conveyor belt or a stirring channel. Deepuée of extrusion, the hot mass is rolled and cooled, for example in a cooling band. When it has solidified, the maea ee breaks and then it is ground. Convenient milling units are disc mills with pastree, ultracentrifugal mills, jet mills and especially sorting mills. The powder can be subsequently classified and preferably screened. If desired, they may be mixed with added substance in the prior sieving powder, for example, talar antitort agent such as metallic flake pigments or silica. The powder coating compositions of this invention preferably have an average particle size of 5 μm to 100 μm and more preferably 30 μm to 50 μm. Another technique for the preparation of revetment in poivo (EP-B-368 851 or WO-A-92/00342) has recently been described, which can also be used for this invention. In these techniques, the premixed or extruded formulation is fed to a heated rotating tube and centrifuged on a rotating plate. At the edge of the plate, round, virtually monodisperse droplets form, which solidify in cooled air before falling into a hopper. A recent technique for preparing powder coating powders is described in EP-A-661 091 and WO-A-94/009 913. Here, all components of the powder coating formulation are mixed together in the presence of a supercritical liquid that is preferably carbon dioxide. The mixture is sprayed with fine jets so that rounded particles of powdery paint of the required size are given when the carbon dioxide evaporates instantaneously. In cases where the component (2) of the powder coating compositions according to this invention is already a solid of very low melting point (<50 ° C) or liquid, problems may arise to handle, since products Sticky or liquid can not be easily mixed and fed to an extruder. Difficulties can also arise when component (2) is a solid with a high melting point (> 120 ° C) or with high melting viscosity at extrusion temperatures, since these products are often not completely homogenized in the resin when extruding. In such cases, it has been found useful to use component (2) of this invention in the form of a maeetro batch. A masterbatch, essentially, is a concentrate of component (2), or preferably, dissolved in one of the layered components forming the component (1), such as polyester, epoxy resin or polyacrylate. The amount of additives that the masterbatch can contain is limited only by solubility conditions and the physical properties of the masterbatch, such as the tendency to form cake when storing. The values may vary from 5-90% preferably 5-60%, more preferably 5-40% and in particular 5-30% of the component (2) in a master batch. For all types of resins, a masterbatch may be prepared at some stage during the resin synthesis. For example, in the case of polyesters that are usually prepared at a temperature of approximately 240 * 0, the component (2) can be conveniently and preferably dissolved in the hot resin after the synthesis during the cooling cycle. If an extruder is used to produce the masterbatch, then of course the other reactive component of the powder coating is omitted which can be used if a higher melting temperature is desired. Other powder coating components such as flow aids, degassing agents, etc. , they can be incorporated in the master batch of the component (2) if it is convenient. A further preferred embodiment of this invention is a masterbatch comprising a polyester, an epoxy resin or a polyacrylate and at least two different compounds containing a residue of the formula (A). An alternate method for using component (2) or powder coatings according to this invention is in an absorbed form in a porous solid. This is particularly useful if the component (2) turns out to be a resinous liquid or solid at room temperature. The amount of component (2) that can be absorbed in the absorbent is limited only by the need for the final product to be in the form of a free flowing powder, such as a powder that can easily be mixed together with the other components of the powder coating formulation before extrusion. For this purpose in general, an absorber having a high oil absorbance value is chosen, together with a low particle size to reduce matte finish: suitable absorbents are alumina and silica in particular. The following examples illustrate the invention in more detail. The parts and percentages are given by weight unless otherwise stated.
Derivatives 2.2.6.6-Tetramethylpioeridine (hindered amines) in Examples 1 to 6: Compound (ia-l: (Tinuvin "" 144) Compound tla-21; (Tinuvin "" 292) Co u sto f.Ia-3): (Tinuvin "" 770) Compound fIa-6): compues o (Ib-i): (Mark "" LA62) H ^ - CH - CH - CH3 R R R R where radicalee R is -C00-C ?: jH27 and in a ratio of 1.7: 2.3. Compound f11-11: (Chimassorb "" 119 FL (ground at 100-250 μ)) HN - (CH 2) 3 - N - (CH 2) 2 - N - (CH 2) 3 - NH R R R R with R that is the group Compoteto (IX-21: (Mark "" LA6) with s that is a number from 1 to 20, Compoteto (XII-ll: (Tinuvin "* 622LD) with b6 which is a number from 2 to 25, Compound (XI11-1): (Sanduvor "" PR3l) Compu sto (X1V-1) (Sanduvor "" 30 6) Example 1: The formulations listed in Table 1 are extruded once at 110"c and 300 rpm, using a Prie extruder adapted with an eetandard loop Table 1: Formulation Quantities in g 1 2 3 __ Crylcoat" "430 366.4 366.4 366.4 366.4 Tabia 1: f Cont.1 Formulation Quantities in g. 4 ("" UCB SA) Polymer functionalized polyester Araidit "" PT 810 27.6 27.6 27.6 27.6 ("" Ciba Specialty Chemicals Inc.) Trigl cidyl isocyanurate Resiflaw "" PV 88 4.0 4.0 4.0 4.0 ("" Worlée Chemie GmbH) Fiox auxiliary T02"" Kronos 2160 200 200 200 200 ("" Kronos-Titan GmbH) Benzoin 2 2 2 2 Degassing agent Compound (II-1) 12 6 Compound (XII-1 ) 12 6 Total: 600 612 612 612 The melt is coiled and coarsely milled using a table cutter The formulations are then finely milled using an ultracentrifugal mill "Retsch Z -1 at 15,000 rpm, using a grinder sieve. 0.25 m.A. The resulting powder is screened through a 125 μm sieve for a polypropylene coating with an average particle size of 32 μm. The triboelectric load is determined using a triboelectric load measuring apparatus developed by and obtained from Professors 11. Bauch and W. Kleber of Dresden, Germany. The instrument that is fully described in the literature (document presented by Kleber and Lang at the 9th International Electro-Static Conference, York, 2-5 April 1995 (Inst. Phys. Conf. Ser. No. 143, pages 201 - 204), It uses a PTFE loading tube with an internal diameter of 2 mm, with a PTFE rod of 250 mm, with a diameter of 10 mm fitted inside.In addition to the standard air pressure meter, the device is coupled with a flow meter for Allow the flow of air through the PTFE tube to be precisely checked Compressed, oil-free and dry air at 22"C is used for all measurements of the tripo-electric load at an air flow rate of 1800 L / h Using a sample size of 60 g, the measurements of the total load (in μC) are generated and the time of flow through the loading tube is carried out, from these values, the load / mass ratio (in μC / kg) ee calculated for each sample. you, all are in the range 160-200 g / min.
Table 2: Formulation Hindered amine charge / mass ratio ftfC / kg) 1 none 170 2 Compound (II-1) 1580 3 Compound (XII-1) 1080 4 Mixture 1: 1 of compounds - 1770 (II-1) y ( XII-1) The results illustrated in Table 2 clearly reveal a synergistic effect for the mixture of compounds (II-1) and (XII-1) in comparison with the simple compounds at the same total concentration of hindered amine. Example 2; Instead of the compound (XII-l) in Example 1, the compound (la-3) is used to give the formulations 5 and 6. The powders are prepared and measured exactly in the same manner as described in Example 1. The results obtained are illustrated in Table 3. Table 3: Formulation Amine hindered charge ratio / E & mass iuC / ka none 170 2 Compound (1-3) 680 3 Compound (II-1) 1580 Table 3: (Cont.) Formulation Impaired amine load ratio / 4 Compound 1: 1 mixture - 1770 (1-3) and (II-1) The results illustrated in Table 3 again reveal a synergistic effect for the mixture of compounds (1-3) and (II-1) in comparison with the simple compounds at the same total concentration of hindered amine. Example 3? The general formulation illustrated in Table 4 is used for the preparation of powder coatings based on a polyacrylate functionalized with Cflicidyl-m, ethacrylate (GMA resin): Table 4: Component Quantities in a. Almatex "" PD 7690 157.4 ("" Mitsui Chemicals Europe GmbH) resin-GMA 1,12-dodecanoic Acid 38.6 ("" Du Pont de Nemours Inc.) Interlacing agent Resi low "" PV88 3 ("" Worlée Chemie GmbH) Table 4: (Cont.) Component Quantities in a. Flow aid Benzoin 1 Gassing agent Ti02"" Bayer R-KB-5 100 Hindered amine from Table 5 1.5 Table 5: Folation NQ. Hindered amine 1 None 2 Compound (Ib-1) 3 Compound (IX-2) 4 Compound (VIII-1) Compound (XIV-1) Compound (la-6) Compound (Ia-2) 8 Compound (Ia- 1) 9 Mix 1: 1 of the compounds (lb-1) and (la-1) Mix 1: 1 of the compounds (IX-2) and (Ia-1) 11 Mix 1: 1 of the compounds (1X-2) and (la-6) 12 Mix 1: 1 of the compounds (XIII-1) and (Ia-1) 13 Mix 1: 1 of the compounds (XI1I-1) and (la-6) 14 Mix 1: 1 of the compounds (XIV-1) and (la-6) Mixture 1: 1 of the compounds (Ia-2) and (la-6) Tabía 5: ícont.) Formulation No. Amine impedidafs) 16 Mixture 1: 1 of the compounds (Ia-1) and (la-6) 17 Mix 1: 1 of the compounds (IX-2) and (XIII-1) The formulations are mixed together well and then extruded in doe paeoe at 90 ° C using a Prism extruder. The extruded formulations are paened through cooling rollers, left to cool, broken with a rolling pad in a polyethylene bag and then milled at 10,000 rpm using a Retsch "" ZM-1 ultracentrifugal mill coupled with a slip ring and the grinding sieve in 1.5 mm. The powder is finally sieved on a rotary screen through 125 μm. The particle size of the powders is approximately 31 μm. In the case of formulations 8, 9, 10, 12 and 16, compound (Ia-1) is used in the form of a masterbatch. This is prepared by mixing 19 parts of the Almatex "" resin with 1 part of the compound (Ia-1) and formulating at 145 ° C in the Prism extruder. The amount of the Almatex resin in these formulations is then adjusted according to ensure the relationship or ratio of binder / crosslinker, and the complete formulation with the other components extruded again in the normal way. The loading properties of the powders are measured in the manner previously described in Example 1. The results are illustrated in Table 6.
Table 6: Formulation Hindered amine load ratio / 1 none 472 2 Compound (Ib-1) 722 3 Compound (IX-2) 717 4 Compound (VIII-1) 689 5 Compound (XIV-1) 733 6 Compound (la- 6) 750 7 Compound (Ia-2) 783 8 Compound (Ia-1) 694 9 Mixture 1: 1 of the compounds- (Ib-1) and (Ia-1) 733 10 Mixture 1: 1 of the compounds- ( IX-2) and (Ia-1) 733 11 Mixture 1: 1 of the compounds- (IX-2) and (la-6) 767 12 Mixture 1: 1 of the compounds (XIII-1) and (Ia-1) ) 711 13 Mixture 1: 1 of the compounds- (XIII-1) and (la-6) 756 Table 6: ÍCant. Formulation Amine hindered load ratio / M? m sa (μC / kg) 14 Mixture 1: 1 of the compounds- (X1V-1) and (la-6) 756 15 Mixture 1: 1 of the compounds- (Ia-2) and (Id-6) 800 16 Mixture 1: 1 of the compounds- (Ia-1) and (la-6) 772 17 Mixture 1: 1 of the compounds- (IX-2) and (XIII-1) 739 The results illustrated in Table 6 clearly reveal a synergistic effect to the mixture in comparison with the simple compounds in the same total concentration of hindered amine. Example 4: A preferred mixture of two hindered amines is a 50:50 mixture of the compounds (II-1) and (Xl-1) which have been melted together. This is sold commercially by "" Giba Speciaiity Chemicals with Tinuvin "" 111. The particular product form used in this example is Tinuvin "" 111 FD, which is in the form of a powder nodule with an approximate size of 2 mm. Powdered preparations prepared using this mixture of hindered amines, according to the formulation described in Table 7, show that excellent triboelectric charge capacity can be imparted to seams which are interlaced with isocyanate chemistry. Tabja 7: Formüiacign Quantities in a. 1 2 3 Crylcoat "" 240 869.4 869.4 869.4 ("" UCB SA, Drogenbos, Belgium) Vestagon hydrauy-functionalized polyester "" BF 1540 118.6 118.6 118.6 ("" Hüls AG, Mari, Germany) uretdione entangling agent Reeiflow "" PV88 10 10 10 ("" Worlée GmbH, Lauenburg, Germany) Flow aid Benzoin 2 2 2 ("" Fluka AG, Buche, Switzerland "" Bayer Titan R-KB-5 500 500 500 ("" Bayer AG, Le erkusen , Germany) Tinuvin "" 111 FD 0 5 10 ("" Ciba Specialty Chemicals, Basel, Switzerland) Total 150 1505 1510 The formulations are mixed well and then extruded in two steps at 80"C using a Buss extruder" "PLK 46L at 125 rpm, the extruded formulations are then milled in a Retsch ultra-centrifugal mill and screened.The average particle size is approximately 44 μm.The properties of the tripo-electric charge of the powders are measured in the manner previously described in FIG. Example 1The results are illustrated in Table 8. Table 8: Formulation Tinuviir Concentration * 111 Ratio of No. FD in total resin (%) load / mass (μCAg) 1 0 467 2 0.5 1039 3 1.0 1100 Example 5: Similar to Example 4, it can be shown that the mixture of hindered amines commercially sold as Tinuvin "" 111 FD is well suited for improving the triboelectric chargeability of a hybrid polyester / epoxy powder paint. For this purpose, the formulations described in Table 9 are constituted.
Table 9: Formulation Quantities in g. 1 2 3 4 5 Crylcoat "" 360 577.8 577.8 577.8 577.8 577.8 ("* UCB SA, Drogenboe, Belgium) functionalized polyether-carboxy Araldit" "GT 7004 385.2 385.2 385.2 385.2 385.2 (" "Ciba Speciaiity Chemicale, Baeel, Switzerland) Reeina Araidit epoxy "" DT 3126 25 25 25 25 25 ("" Ciba Specialty Chemicale, Basei, Switzerland) Resiflow catalyst masterbatch "" PV88 10 10 10 10 10 ("" Worlée Chemíe GmbH, Lauenburg, Germany) Flow aid Benzoin 2 2 2 2 2 ("" Fluka AG, Buchs, Switzerland) Bayer "" Titan R-KB-5 500 500 500 500 500 ("" Bayer AG, Leverkusen, Germany) Tinuvin "" 111 FD 0 5 10 15 20 Table 9: (Cont. ) Formulation Quantities in a. 1 2 3 4 5 ("" Ciba Specialty Chemicals, Basel, Switzerland) Total 1500 1505 1510 1515 1520 The formulations are mixed well and then extruded in two passes at 80 ° C using a Buss "" PLK 46L extruder at 125 rpm. The extruded formulations are then milled in a Retsch "" ZM-1 uitracentrifugal mill and sieved. The average particle size is approximately 43 μm. The triboelectric charge properties of the powders are measured in the manner previously described in Example 1. The results are illustrated in Table 10. Table 1P; Formulation Tinuvin Concentration * ß 111 Ratio of No. FD in total of resins (%) load / mass (μC / kg) 1 0 172 2 0.5 794 3 1.0 978 4 1.5 1039 5 2.0 1133 In addition, it can be shown that the mixture of aminae impedidae sold commercially as Tinuvín "" i11 FD is well suited to improve the triboelectric charging capacity of a polyester powder paint / Araldít "" PT 910. For this purpose, the formulations described in Table 11 are produced. Table 11: Formulation Quantities in q. 1 2 3 4 5 Crylcoat "" 803 918 918 918 918 918 ("" UCB SA, Drogenbos, Belgium) carboxy-functionalized polyester Araldit "" PT 910 69 69 69 69 69 ("" Ciba Speciaiity Chemicals, Basel, Switzerland) Agent Epoxy Interlacing Resiflow "" PV88 10 10 10 10 10 ("" Worlée Chemie GmbH, Lauenburg, Germany) Flow aid Benzoin 3 3 3 3 3 ("" Fluka AG, Buchs, Switzerland) "" Bayer Titan - R-KB -5 500 500 500 500 500 ("" Bayer AG, Leverkusen, Germany) Table 11; (Cont.) Formulation an id des go g "1 2 3 4 5 Tinuvin" "111 FD 0 5 10 15 20 (" "Giba Specialty Chemicals, Basel, Switzerland) Total 1500 1505 1510 1515 1520 The formulations are mixed well and then They are extruded in two passes at 80"c using Buse extruder" "PLK 46L at 125 rpm.The extruded formulations are then milled in a Retsch" "ZM-1 ultracentrifugal mill and sieved.The average particle size is approximately 51 μm. triboelectric charge properties of the powders ee measured in the manner previously described in Example 1. The results are shown in Table 12. Table 12: Formulation Concentration of Tinu.viir '* 111 Ratio of No. FD in total of resins ( %) load / mass (μC / kg) 1 0 217 2 0.5 767 3 1.0 953 4 1.5 1045 5 2.0 1067

Claims (16)

  1. CLAIMS 1. A method for improving the loading capacity of a powder coating composition containing an organic film-forming binder, this method is characterized in that it comprises incorporating in the powder coating composition at least two different corallings containing a recycle. of the formula (A)
    co or electron donadoree.
  2. 2. A method according to claim 1, characterized in that the two different compounds containing a residue of the formula (A) ee and the group consisting of the classes a) a compound of the formula (Ia) or (Ib) )
    wherein Ax is hydrogen, alkyl having 1 to 8 carbon atoms or alkeniion having 3 to 6 carbon atoms, bi is 1, 2 or 4, if bx is 1, A2 is alkyl with 1 to 9 carbon atoms, and ee 2, A2 is aikylene with 1 to 10 carbon atoms or a group of the formula
    wherein R x is alkyl with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, R 2 is alkylene with 1 to 10 carbon atoms and R 3 and R "independently are alkyl with 1 to 4 carbon atoms, cyclohexyl or methylcyclohexyl and if bx is 4, A2 is acycotatray with 4 to 10 carbon atoms; H2C-CH-CH-CH2 (Ib) I I I R R R R wherein the radicals R independently of one another are -COO- (alkyl having 1 to 20 carbon atoms) or a group
    with Ai which is as defined above; b) a compound of the formula (II) (II)
    wherein A3 and A7 independently of each other are hydrogen or alkyl having 1 to 12 carbon atoms, A ", A5 and A6 independently of each other are alkylene © with 2 to 10 carbon atoms and Tx, T2, T3, T4, T5, T6, T7 and Tß independently of each other are a group of the formula (III)
    wherein A8 is hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, cycloalkyl having 5 to 12 carbon atoms eubstituted with alkyl having 1 to 4 carbon atoms, phenyl or a group of the formula (IV)
    and A »and Aio independently of each other are as defined for Ax; c) a compound of the formula (V)
    wherein T9 Txo and TX1 independently represent a group of the formula (III); d) a compound of the formula (VI)
    wherein Au / A13 Al4 and A15 independently of one another are hydrogen, aikyl with 1 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms substituted with alkyl having 1 to 4 carbon atoms , phenyl or a group of the formula (IVj, A ^ is alkylene with 2 to 10 carbon atoms, cycloalkylene with 5 to 7 carbon atoms or alkylene with 1 to 4 carbon atoms-di (cycloalkylene with 5 to 7 carbon atoms) carbon), or the radicals All t AX2 and A13, together with the nitrogen atom to which they are connected, form a heterocyclic ring of 5 to 10 members or A14 and A? S together with the nitrogen atom to which they are bound, form a heterocyclic ring of 5 to 10 members, b2 is a number of 2 to 50 and at least one of the radicals Au, A13, A14 and A15 is a group of the formula (IV): e) a compound of the formula (VII) )
    wherein Al6 is alkyl with 1 to 10 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, cycloalkyl with
    5 to 12 carbon atoms substituted with alkyl with 1 to 4 carbon atoms or phenyl, A17 is alkylene with 3 to 10 carbon atoms, Aa8 is as defined for Ax and s is a number from 1 to 50; f) a product that is obtained by reacting an intermediate product, which is obtained by reacting a polyamine of the formula (VII-a) with cyanuric chloride, with a compound of the formula I12N - (CH2) b4, - NH - ( CH2) b4. - NH - (CH2) b4., - NH2 (VHI-a) where b *, b4 »and b4», independently of each other are a number from 2 to 12, Ai, is hydrogen, alkyl with 1 to 12 carbon atoms , cycloalkyl with 5 to 12 carbon atoms or phenyl and A20 is as defined for Ax; g) a compound of the formula
    (IX)
    wherein A2X, A22, A23, A24 and A2S independently of each other represent a direct bond or alkylene with 1 to 10 carbon atoms, A ^ is as defined for Ax and bs ee a number from 1 to 50; h) a compote of the formula (X) O
    (X) IAO 13
    wherein T12, T13 and T14 independently of each other are a group of the formula (XI) - CH2 - CH ~ CH2 - L (XI) I
    OH wherein L is a group of the formula (III); i) a compound of the formula (XII)
    wherein A27 is hydrogen or methyl, A28 is a direct bond or alkylene with 1 to 10 carbon atoms and bg is a number of 2 to 50; j) a compound of the formula (XIII)
    wherein A27 is hydrogen or methyl, A2β is a direct bond or alkylene with 1 to 10 carbon atoms and b6 is a number of 2 to 50; j) a compound of the formula (XIII)
    wherein A29 is as defined for Aa and JO is hydrogen, alkyl having 1 to 12 carbon atoms or alkoxy with 1 to 12 carbon atoms; kj a compound of the formula (XIV)
    wherein A31 is alkyl with 1 to 24 carbon atoms and A32 ee as defined for Ax; and 1) a compote of the formula (XV)
    wherein A33 is as defined for Ai and A34 is alkyl with 1 to 20 carbon atoms or alkenyl with 2 to 20 carbon atoms.
  3. 3. A method according to claim 2, characterized in that Ai is hydrogen or alkyl with 1 to 4 carbon atoms, bi ee 2 or 4, ei hx ee 2, A2 is alkylene with 2 to 8 carbon atoms or a group of the formula
    if bi is 4, A2 is 1, 2, 3, 4-butantetrail, the R radicals independently of each other are -C00-Ci3H27 or a group
    A3 and A7 independently of one another are hydrogen or aikyl with 1 to 4 carbon atoms, A4, As and A6 independently of each other are alkylene with 2 to 3 carbon atoms, Tt t T2,
    T3, T4, T5, T6, T7 and T8 independently of each other are a group of the formula (III), wherein A8 is hydrogen, aikyl with 1 to 4 carbon atoms or a group of the formula (IV), An, A 3, A 4 and Ais independently of one another are hydrogen, alkyl having 1 to 8 carbon atoms, cyclohexyl or a group of the formula (IV), Ai 2 is alkylene with 2 to 10 carbon atoms or AX 4 and Ais together with the nitrogen atom to which they connect form morpholino, b2 is a number from 2 to 25, A? 6 is alkyl with 1 to 4 carbon atoms, cyclohexyl or phenyl, Ai7 ee alkylene with 3 to 8 carbon atoms, b-, is a number from 2 to 25, b4 ', b4"and b4"' independently of each other are a number from 2 to 3, A19 is hydrogen or alkyl with 1 to 4 carbon atoms, A2i, A23, A24 and A25 independently between yes they are alkylene with 1 to 4 carbon atoms, A22 is a direct bond, b5 is a number from 1 to 20, A28 is alkylene with 2 to 8 carbon atoms, b6 is a number from 2 to 25, A30 is aoxy with 1 to 4 carbon atoms, A3X is C2H2s and A34 is alkyl with 12 to 14 carbon atoms.
  4. 4. A method according to claim 2, characterized in that the two different compounds contain a residue of the formula (A) are not covered by the same class.
  5. 5. A method according to claim 1, characterized in that the two different compounds containing a residue of the formula (A) are selected from the group consisting of the compounds of the formulas (Ia-1), (Ia-2) , (Ia-), (Ia-4), (Ia-5), (la-6), (Ib-1), (Ib-2), (II-l), (VI-1), (VI) -2), (VI-3), (VI1-1), (VIII-1), (IX-1), (IX-2), (XII-1), (XIII-1) and (XIV-1) )
    H, C - CH CH - CHa (Ib-1)
    R R R R where the radicals R are -C00-C? 3H27 and
    in a ratio of 1.7: 2.3. H2C - CH - CH - CH2 (Ib-2)
    R R R R wherein the radicals R are -C00-C13H27 and in a ratio of 1.7: 2.3, HN- (CH2) 3 -N- (CH2) 2 -N- (CH2) 3 -NH (II-1)
    R R R R with R which is the group
    with b2 which is a number from 2 to 25,
    with b3 which is a number from 2 to 25, a product (VIII-1) which is obtained by reacting an intermediate product, which is obtained by the reaction of the polyamine of the formula H ^ - (CH2) 3-NH- ( CH2) 2-NH - < CH2) 3-NH2 with cyanuric chloride, with the compound of the formula
    (IX-D (IX-2.). Faith that is a number from 1 to 20,
    with bs that is a number from 2 to 25,
  6. 6. A method according to claim 5, characterized in that the two different compounds containing a residue of the formula (A) are selected from the group consisting of the compounds of the formulae (Ia-1), (Ia-2), ( Ia-3), (la-6), (Ib-1), (Il-i), (IX-2), (XII-1), (XIII-1) and (XIV-1).
  7. 7. A method according to claim 5, characterized in that the two different compounds containing a residue of the formula (A) are chosen from the group consisting of the compotetoe of the formula (Ia-1), (Ia-2), ( Ia-3), (la-4), (Ia-5), (II-1), (VI-1), (XII-1) and (XIII-1).
  8. 8. A method according to claim 5, characterized in that the two different compounds containing a residue of the formula (A) are the compounds of the formulas (II-1) and (Vl-1), the compounds of the formulas (II-1) and (XII-1), the compotetoe of the formulas (la-1) and (Ia-3), the compuets of the formulas (Ia-2) and (II-1) or the compueetos of the Formulae (Ia-3) and (II-1).
  9. 9. A method according to claim 1, characterized in that the organic film-forming binder is a polyester or polyacrylate resin together with an entangling agent or an epoxy resin or combinations of resin.
  10. 10. A method according to claim 9, characterized in that the entanglement agent is an epoxy, triglycidyl-isocyanurate, glycoluril, hydroxyalkylamide, uretdione or blocky epoxy.
  11. 11. A powder coating composition, containing 1) an organic film-forming binder and 2) at least two different compounds containing a residue of the formula (A)
    as electron donors, characterized in that the powder coating composition has a charge / mass ratio of at least 200 μC / kg.
  12. 12. A poiv coating composition according to claim 11, characterized in that the powder coating has a charge / mass ratio of 200 μC / kg to 10 000 μC / kg.
  13. 13. A method for loading a powder coating composition containing 1) an organic film-forming binder and 2) at least two different compounds containing a residue of the formula (A)
    as electron donors, this method comprises charging the powder coating composition with a charge / mass ratio of at least 200 μC / kg in a tribocharge gun.
  14. 14. A method for applying triboelectrically to a metal substrate, a powder coating composition containing 1) an organic film-forming binder and 2) at least two different compounds containing a residue of the formula (A)
    as electron donors.
  15. 15. A powder coating composition, characterized in that it contains l) an organic film-forming binder, and 2) at least two different compounds selected from the group consisting of the compounds of the formulas (Ia-4), (Ib-1) ), (Ib-2), (II-1), (VI-1), (VI-2), (VI-3), (VII-1), (VIII-1), (IX-1), (IX-2) and (XII-1) as defined in claim 5.
  16. 16. A powder coating composition according to claim 15, characterized in that the two compounds other than component 2) are the compounds of the formulas (II-1) and (XII-1).
MXPA/A/1998/000846A 1997-01-31 1998-01-30 A method for improving the loading capacity of a coating composition in po MXPA98000846A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE97810046.9 1997-01-31
EP97810046 1997-01-31

Publications (2)

Publication Number Publication Date
MX9800846A MX9800846A (en) 1998-10-31
MXPA98000846A true MXPA98000846A (en) 1999-01-11

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