ONE-COMPONENT AMINO RESIN COATING COMPOSITIONS

Abstract

The present invention relates to one-component amino resin coating compositions having good chemical resistance, a good balance of hardness to elasticity, and rapid drying, to their use, and to methods for coating. Synthesis components that the coating compositions comprise include amino resin, hydroxyl-containing polymers as principal polyols, and certain branched polyester polyols, obtainable by polycondensation of hexahydrophthalic anhydride, trimethylolpropane, and optionally further components.

Claims

1: A one-component amino resin coating composition, comprising as synthesis components (A) at least one amino resin selected from the group consisting of a melamine-formaldehyde resin, a benzoguanamine-formaldehyde resin, and a urea-formaldehyde resin, (B) at least one hydroxyl-containing polymer selected from the group consisting of a poly(meth)acrylate polyol (B1), a polyester polyol (B2), a polyetherol (B3), an alkyd resin (B4), and a polycarbonate polyol (B5), (C) at least one branched polyester polyol prepared by polycondensation of hexahydrophthalic anhydride, trimethylolpropane, optionally at least one diol, optionally at least one further triol, and optionally at least one further diacid or triacid or a derivative thereof, where a molar ratio of acid groups to hydroxyl groups in preparing the polyester polyol is 1:1 to 1:1.95, the polyester polyol contains less than 20% tetraalcohol stoichiometrically relative to hexahydrophthalic anhydride, and the polyester polyol is not formed from dihydroxycarboxylic acids, (D) optionally at least one chemical crosslinker selected from the group consisting of a blocked polyisocyanate, a trisalkylcarbamoyltriazine, an epoxy resin, a carboxyl-containing resin, and an amino-containing resin other than the amino resin (A), (E) optionally at least one organic solvent, (F) optionally at least one catalyst, (G) optionally at least one coating additive, and (H) optionally at least one filler, dye and/or pigment, wherein a ratio of (B) to (C) is greater than 1:1 based on solids.

2: The coating composition according to claim 1, wherein the amino resin (A) is a partly etherified melamine-formaldehyde resin which has a molar melamine:formaldehyde:alcohol incorporation ratio of 1:3 to 5.4:1.5 to 4.3.

3: The coating composition according to claim 1, wherein the amino resin (A) is a fully to highly methylolated and fully to highly alkylated melamine-formaldehyde resin which has a molar melamine:formaldehyde:alcohol incorporation ratio of 1:greater than 5.5:greater than 4.5.

4: The coating composition according to claim 1, wherein the hydroxyl-containing polymer (B) is a poly(meth)acrylate polyol (B1) having a number-average molecular weight M.sub.n of 500 to 50 000 D.

5: The coating composition according to claim 1, wherein the polymer (B) and the branched polyester polyol (C) are used in a weight ratio of 1.1:1 to 49:1, based on solids.

6: The coating composition according to claim 1, wherein the polyester polyol (C) has a hydroxyl number of 130 to 280 mg KOH/g based on solids and/or the polyester polyol (C) has an acid number of 8 to 110, according to DIN EN ISO 2114:2000, based on solids, and/or the polyester polyol (C) has a sum total of acid number according to DIN EN ISO 2114:2000 and hydroxyl number according to DIN 53240-2:2007-11 of 200 to 400 mg KOH/g.

7: The coating composition according to claim 1, wherein the polyester polyol (C) is prepared exclusively from hexahydrophthalic anhydride and trimethylolpropane in a molar mixing ratio of acid groups to hydroxyl groups of 1:1.1 to 1:1.6.

8: The coating composition according to claim 1, wherein the polyester polyol (C) is prepared by not using, apart from hexahydrophthalic anhydride, any further diacid or triacid or a derivative thereof.

9: The coating composition according to claim 1, wherein the polyester polyol (C) is formed exclusively from hexahydrophthalic anhydride, trimethylolpropane, and at least one diol of an isomer or an isomer mixture of tricyclodecanedimethanol, tetrahydro-2,5-bis(hydroxymethyl)furan, 1,6-hexanediol, neopentyl glycol, and 2-butyl-2-ethyl-1,3-propanediol.

10: The coating composition according to claim 9, wherein a molar ratio of the hydroxyl groups of trimethylolpropane to the hydroxyl groups of the at least one diol is greater than 1:1.

11: The coating composition according to claim 1, wherein the polyester polyol (C) is tin-free and/or is prepared uncatalyzed or with a catalyst comprising zinc, titanium, zirconium, or bismuth, or with another catalyst not comprising tin, and/or wherein the polyester polyol (C) is prepared in the absence of solvent.

12: The coating composition according to claim 1, wherein the polyester polyol (C) has a number-average molecular weight Mn of 500 to 4000 g/mol and/or has a polydispersity of less than or equal to 5.

13: The coating composition according to claim 1, wherein the polyester polyol (C) has a glass transition temperature of 20 to 50 C.

14: The coating composition according to claim 1, wherein the polyester polyol (C) is prepared in a one-stage procedure.

15: The coating composition according to claim 1, which comprises the synthesis components in the following amounts: (A) 100 parts by weight of the amino resins, based on solid fraction; (B) from 45 to 882 parts by weight of the hydroxyl-containing polymer, in each case based on solid fractions; (C) from 2 to 450 parts by weight of the branched polyester polyol, in each case based on solid fractions; (D) optionally the chemical crosslinker; (E) from 0 to 80 wt % of the organic solvent, based on a sum total of the components (A) to (G); (F) from 0 to 10 parts by weight of the catalyst, based on the amino resin (A) used (solid on solid); (G) optionally the coating additive; and (H) optionally the filler, dye and/or pigment.

16: A method for coating a substrate, the method comprising: mixing an amino resin (A), a polymer (B), and a polyester polyol (C), in optionally a chemical crosslinker (D), optionally at least one organic solvent (E), optionally at least one catalyst (F), optionally at least one coating additive (G), and optionally at least one filler, dye, and/or pigment (H), to obtain a mixture, and subsequently applying the mixture to the substrate, wherein the amino resin (A) is at least one selected from the group consisting of a melamine-formaldehyde resin, a benzoguanamine-formaldehyde resin, and a urea-formaldehyde resin, the polymer (B) is at least one hydroxyl-containing polymer selected from the group consisting of a poly(meth)acrylate polyol (B1), a polyester polyol (B2), a polyetherol (B3), an alkyd resin (B4), and a polycarbonate polyol (B5), the polyester polyol (C) is at least one branched polyester polyol prepared by polycondensation of hexahydrophthalic anhydride, trimethylolpropane, optionally at least one diol, optionally at least one further triol, and optionally at least one further diacid or triacid or a derivative thereof, where a molar ratio of acid groups to hydroxyl groups in preparing the polyester polyol is 1:1 to 1:1.95, the polyester polyol contains less than 20% tetraalcohol stoichiometrically relative to hexahydrophthalic anhydride, and the polyester polyol is not formed from dihydroxycarboxylic acids, and the chemical crosslinker (D) is at least one selected from the group consisting of a blocked polyisocyanate, a trisalkylcarbamoyltriazine, an epoxy resin, a carboxyl-containing resin, and an amino-containing resin other than the amino resin (A).

17: A method for coating, comprising: applying the coating composition according to claim 1 to a part of a building, a vehicle, an aircraft, a can, a coil, or a decorative coating system.

18: A method for coating a substrate, the method comprising: applying the coating composition according to claim 1 to the substrate, which is wood, wood veneer, paper, paperboard, cardboard, textile, film, leather, nonwoven, a plastics surface, glass, ceramic, a metal, or a mineral building material, wherein the substrate is precoated or pretreated.

19: A substrate, coated with the coating composition according to claim 1.

Description

EXAMPLES

[0152] Substances used in the examples:

TABLE-US-00001 Hexahydrophthalic Aldrich. m.p. 33 C. Is melted in an oven before use anhydride Dimethyl adipate Aldrich. Liquid Trimethylolpropane Aldrich. White flakes, melting point 56-58 C. Neopentyl glycol Solid, m.p. 127 C. 2-Butyl-2-ethyl- TCI (Tokyo Chemical Industry). Melting point 1,3-propanediol 43 C.; is melted over a waterbath before use Joncryl 504: Polyacrylate-ol, OH number 140 mg KOH/g, 80% solids content in xylene; BASF SE, Ludwigshafen Dynapol Branched polyester polyol, 60% in solvent naphtha LH 832-02 150/butyl glycol Luwipal 018: n-Butanol etherified melamine-formaldehyde resin in n-butanol especially for automotive applications. 73% NVF (2 g/2 h/125 C.). 5.5 Pa*s (23 C.). BASF SE Luwipal Methanol etherified melamine-formaldehyde resin in 066 LF: methanol (HMMM resin). 94.5% NVF (2 g/2 h/125 C.). 4.0 Pa*s (23 C.). BASF SE Nacure 2500: Amine-neutralized para-toluenesulfonic acid. Blocked catalyst. King Industries Nacure 2558: Blocked para-toluenesulfonic acid Solvenon PM 1-Methoxy-propan-2-ol, solvent, BASF SE Solvesso 150 ExxonMobil Chemical, aromatic solvent, b.p. 180-193 C.

[0153] Hydroxyl numbers of the branched polyesterols are determined on the basis of

[0154] DIN 53240-2:2007-11. The acid number is taken into account in the calculation.

[0155] Acid numbers of the branched polyesterols are determined according to

[0156] DIN EN ISO 2114:2000, Method A.

[0157] Unless otherwise indicated, the figures for polydispersity and also for number-average and weight-average molecular weight M.sub.n and M.sub.w refer to measurements by gel permeation chromatography, using polymethyl methacrylate as standard and tetrahydrofuran as eluent, with the parameters specified in the examples. Molar masses and polydispersities are determined by gel permeation chromatography with TV-certified PMMA standards from PSS (Polymer Standards Service; DIN EN ISO 9001:2000, certificate: 01 100 84065). These standards are characterized according to the requirements of DIN 55672 and ISO/EN 13885.

[0158] GPC takes place using:

[0159] Instrument: PSS Agilent Technologies 1260 Infinity

[0160] Columns: 1PLGel Mixed E Guard (precolumn), length 5 cm, diameter 0.75 cm [0161] 1PLGel Mixed E, length 30 cm, diameter 0.75 cm [0162] 1PLGel Resipore, length 30 cm, diameter 0.75 cm

[0163] Solvent: THF

[0164] Flow rate: 1 mL/min

[0165] Injection volume: 50 L

[0166] Concentration: 1 g/L

[0167] Temperature: room temperature (20 C.).

[0168] Unless otherwise indicated, the glass transition temperature T.sub.g in this specification is determined according to ASTM D3418-03 via differential scanning calorimetry (DSC), with a heating rate of 10 C./min.

[0169] Viscosities are reported in this specification at 23 C. according to DIN EN ISO 3219/A.3 in a cone/plate system with a shear gradient of 1000 s.sup.1, unless otherwise noted.

[0170] The nonvolatile fraction (NVF) was determined according to the thermogravimetric principle, with the aid of a HB43-S Moisture Analyzer from Mettler Toledo. For this purpose, approximately 2 g of the sample were weighed out into an aluminum sample pan having a diameter of 90 mm (HA-D90) and heated at 150 C. to constant weight.

Synthesis Examples

[0171] In laboratory experiments, trimethylolpropane and neopentyl glycol were introduced as solids to the reactor. Hexahydrophthalic anhydride and 2-butyl-2-ethyl-1,3-propanediol were added in the melted state.

Example B1

[0172] Hexahydrophthalic Anhydride/Trimethylolpropane/Neopentyl Glycol=1.0:0.5:0.5

[0173] In a four-neck flask with reflux condenser and water separator, trimethylolpropane (490.9 g), neopentyl glycol (381.0 g), and hexahydrophthalic anhydride (1128.1 g) were introduced under a nitrogen atmosphere and heated to 160-180 C. with stirring. After a reaction time of 5 hours and on attainment of an acid number of 85 mg KOH/g (80% conversion), the batch was cooled to 120 C., 631.3 g of butyl acetate were added, and cooling was continued.

Example B2

[0174] Hexahydrophthalic Anhydride/Trimethylolpropane=1.2:1.0

[0175] In a four-neck flask with reflux condenser and water separator, trimethylolpropane (840.8 g) and hexahydrophthalic anhydride (1159.2 g) were introduced under a nitrogen atmosphere and heated to 160-180 C. with stirring. After a reaction time of 5 hours and on attainment of an acid number of 83 mg KOH/g (81% conversion), the batch was cooled to 120 C., 1017.1 g of butyl acetate were added, and cooling was continued.

Example B3

[0176] In a four-neck flask with water separator, trimethylolpropane (930.7 g) and hexahydrophthalic anhydride (1069.3 g) were introduced under a nitrogen atmosphere at room temperature, and fully melted, and the melt was heated gradually to 160-180 C. with stirring. After a reaction time of about 5 hours and on attainment of an acid number of 74 mg KOH/g (82% conversion), the batch was cooled to 120 C., 814 g of butyl acetate were added, and cooling was continued.

Example B4

[0177] Hexahydrophthalic Anhydride/Trimethylolpropane/Dimethyl Adipate=1.0:1.5:0.5 with Tetrabutyl Orthotitanate as Catalyst

[0178] In a four-neck flask with water separator, trimethylolpropane (778.0 g), hexahydrophthalic anhydride (596.0 g), and tetrabutyl orthotitanate (0.5 g) were introduced under a nitrogen atmosphere and heated to 160-180 C. with stirring. After a reaction time of 10 hours and on attainment of an acid number of 42 mg KOH/g, dimethyl adipate (337.0 g) was added at 140 C. After a further 10 hours at 180 C., with an acid number of 22 mg KOH/g attained, the batch was cooled to 120 C., 511.0 g of butyl acetate were added, and cooling was continued.

Example B5

[0179] Hexahydrophthalic Anhydride/Trimethylolpropane/2-Butyl-2-Ethyl-1,3-Propanediol=1.2:0.8:0.2

[0180] In a four-neck flask with reflux condenser and water separator, trimethylolpropane (330.9 g), melted 2-butyl-2-ethyl-1,3-propanediol (98.8 g), and hexahydrophthalic anhydride (570.3 g) were introduced under a nitrogen atmosphere and heated to 160-180 C. with stirring. After a reaction time of 5 hours and on attainment of an acid number of 98 mg KOH/g (78% conversion), the batch was cooled to 120 C., 407.0 g of butyl acetate were added, and cooling was continued.

Example B6

[0181] Hexahydrophthalic Anhydride/Trimethylolpropane=1.1:1.0

[0182] In a four-neck flask with reflux condenser and water separator, trimethylolpropane (530.1 g) and hexahydrophthalic anhydride (669.9 g) were introduced under a nitrogen atmosphere and heated to 160-180 C. with stirring. After a reaction time of 5 hours and on attainment of an acid number of 77 mg KOH/g (82% conversion), the batch was cooled to 120 C., 283.3 g of butyl acetate were added, and cooling was continued.

Example B7

[0183] Hexahydrophthalic Anhydride/Trimethylolpropane=1.0:1.0 (with Lower Acid Number)

[0184] In a four-neck flask with water separator, trimethylolpropane (930.7 g) and hexahydrophthalic anhydride (1069.3 g) were introduced under a nitrogen atmosphere and heated to 160 C. with stirring. This temperature was held for about 30 minutes, then raised to 180 C. After a reaction time of about 10 hours and on attainment of an acid number of 54 mg KOH/g, the batch was cooled to 120 C., and the product was diluted to 75% with butyl acetate and cooled further.

Example B8

[0185] Hexahydrophthalic Anhydride/Trimethylolpropane=1.0:1.0 (with Lower Acid Number)

[0186] In a four-neck flask with water separator, trimethylolpropane (465.3 g) and hexahydrophthalic anhydride (534.7 g) were introduced under a nitrogen atmosphere and heated to 160 C. with stirring. This temperature was held for about 30 minutes, then raised to 180 C. After a reaction time of about 8 hours and on attainment of an acid number of 46 mg KOH/g, the batch was cooled to 120 C., and the product was diluted to 70% with 288.4 g of butyl acetate and cooled further.

Example B9

[0187] Hexahydrophthalic Anhydride/Trimethylolpropane/2-butyl-2-ethyl-1,3-propanediol=1.0:0.5:0.5

[0188] In a four-neck flask with water separator, trimethylolpropane (22.6 g), 2-butyl-2-ethyl-1,3-propanediol (265.90 g), and hexahydrophthalic anhydride (511.5 g) were introduced under a nitrogen atmosphere and heated to 160 C. with stirring. This temperature was held for about 30 minutes, then raised to 180 C. After a reaction time of about 4 hours and on attainment of an acid number of 86 mg KOH/g, the batch was cooled to 120 C., and the product was diluted to 75% with 229.3 g of butyl acetate and cooled further.

Example B10

[0189] Hexahydrophthalic Anhydride/Trimethylolpropane/Neopentyl Glycol=2:1.67:1

[0190] In a four-neck flask with water separator, trimethylolpropane (352.0 g), neopentyl glycol (163.6 g), and hexahydrophthalic anhydride (484.4 g) were introduced under a nitrogen atmosphere and heated to 160 C. with stirring. This temperature was held for about 30 minutes, then raised to 180 C. After a reaction time of about 9 hours and on attainment of an acid number of 41 mg KOH/g, the batch was cooled to 160 C. and reduced pressure of 200 mbar was applied for 3 hours. Thereafter the acid number was 35 mg KOH/g. The product was cooled to 120 C. and diluted to 70% with 284.64 g of butyl acetate and cooled further.

Example B11

[0191] Hexahydrophthalic Anhydride/Trimethylolpropane/Neopentyl Glycol=2:1:1.27

[0192] In a four-neck flask with water separator, trimethylolpropane (267.6 g), neopentyl glycol (219.9 g), and hexahydrophthalic anhydride (512.5 g) were introduced under a nitrogen atmosphere and heated to 160 C. with stirring. This temperature was held for about 30 minutes, then raised to 180 C. After a reaction time of about 2 hours and on attainment of an acid number of 62 mg KOH/g, the batch was cooled to 160 C. and reduced pressure of 200 mbar was applied for 1 hour. Thereafter the acid number was 42 mg KOH/g. The reduced pressure was removed, and the product was cooled to 120 C. and diluted to 70% with 285.3 g of butyl acetate and cooled further. Under reduced pressure, some sublimed product had formed in the condenser.

[0193] The B examples are summarized in table 1.

TABLE-US-00002 TABLE 1 Polyester polyols Examples B OHN AN Mn Mw Tg Visco NVF mg KOH/g D D PDI C. Cat. mPa*s % B1 191 85 1032 1438 1.4 17 none 4540 75 B2 188 83 1483 3310 2.2 47 none 3010 65 B3 257 74 1133 1780 1.6 24 none 4010 70 B4 250 22 1798 5339 3.0 4 TBOT 4830 75 B5 158 98 1255 2112 1.7 35 none 4720 70 B6 219 77 1176 2701 2.3 41 none 3110 80 B7 254 49 1568 3709 2.4 36 none 75 B8 239 44 1764 5310 3.0 none 25040 73.7 B9 162 83 1030 1433 1.4 12 none 21500 75 B10 271 33 1136 1589 1.4 20 none 5220 70 B11 198 42 1212 1886 1.6 23 none 7530 70 PDI: Polydispersity; AN: Acid number; OHN: OH number; Visco: Viscosity; Cat.: Catalyst; NVF: Nonvolatile fraction

[0194] Coating Compositions and Comparative Performance Tests:

[0195] The properties tested were as follows:

[0196] The pendulum hardness was determined according to Knig on glass plates (isothermally) or on deep-drawn metal panels (gradient oven 80-180 C.) (DIN EN ISO 1522).

[0197] The development of crosslinking density (chemical resistance) was determined firstly by the methyl ethyl ketone (MEK) double rub test, based on DIN EN 13523-11 and ASTM D5402-06, on a metal Bonder panel. This test took place on a Crockmeter apparatus with a force of 7 newtons, with double rubs until the coating was destroyed. Every 50 double rubs, the felt was moistened with MEK by syringe from the tube above. Felt inserts are for the LINEARTESTER 249 scratch hardness tester from Erichsen.

[0198] The development of crosslinking density (chemical resistance) was determined secondly by the xylene test on a deep-drawn metal panel after curing in a gradient oven at 80-180 C. for 24 hours at a film thickness of 40-50 m. For this purpose, the deep-drawn metal panel was immersed half-way into a xylene bath for 10 minutes, thereafter first rubbed down with a cloth and subsequently scratched with a wooden spatula in order to remove uncured or undercured areas of paint. [0199] 0% curing: The coating is dissolved by xylene or can be wiped off with the cloth [0200] 50% curing: The coating is not removed by xylene and cloth, but can be scratched off using the wooden spatula [0201] 100% curing: The coating is not removed even by the wooden spatula

[0202] The measurement areas on the gradient oven are graduated in approximately 10 C. graduations. In each case the temperature at which 50% or 100% curing was first measured has been reported.

[0203] The Erichsen cupping was determined according to DIN EN ISO 1520 on a deep-drawn metal panel.

[0204] For the determination of the chemical resistance for automobile applications, a coated, deep-drawn metal panel (gradient oven metal panel) was cured for 20 minutes at 140 C. and 16-24 hours (232) C. and (5010) % humidity. Thereafter, using an Eppendorf pipette, drops of the test substances sulfuric acid (1%; 25 l), aqueous sodium hydroxide (1%; 25 l), pancreatin (50 l), and tree resin (25 l) were applied to each heating element (30-75 C.). For the last two agents, every second heating element was missed out. The test panel was then placed into the gradient oven (from BYK Gardner) and thermally conditioned at 30-75 C. for 30 minutes. After the end of this operation, the panel was cleaned to remove the sulfuric acid and the sodium hydroxide solution, using fully demineralized water. The panel was subsequently cleaned with hot water and a soft cloth to remove the adhering pancreatin. Thereafter the tree resin was cleaned, thoroughly but gently, using a soft cloth and wash benzine. Lastly, the panel was washed off thoroughly but gently using cold water, and the remaining drops of water were removed using a soft paper towel. After 24 hours of conditioning at 232 C. and 5010% humidity, evaluation took place. A record was made of the temperature at which the first attack on the coating is perceptible under artificial light.

[0205] Tree resin source: Wrwag, tree resin solution DBL 5416 No.: 701014

[0206] Pancreatin (from Merck. Art. 7130) is mixed 1:1 wt % with fully demineralized water in a porcelain mortar.

[0207] The impact and re-impact tests were conducted according to DIN EN ISO 6272-1. For the impact tester, a falling weight of four pounds and a hemisphere with a 20 mm diameter were used.

[0208] The pencil hardness was determined according to DIN EN 13523-4 with a set of pencils from Cretacolor or Faber Castell (range: 6 B-6 H).

[0209] Test Series 1: Pendulum Hardness with Joncryl 504

[0210] Comparison of mixtures of polyacrylate-ol/inventive polyester polyols B1-B4 with polyacrylate-ol Joncryl 504 without inventive polyester polyols in development of pendulum hardness at 100 C. over a cure time of 10 to 60 minutes in a 7:3 (solid/solid) polyols/Luwipal 018 system. Luwipal 018 is an amino resin typically used in automotive clearcoats. The mixing ratios for Joncryl 504/polyester polyol were 10:0 (reference); 9:1, 8:2, and 7:3 solid/solid. Films were applied to 150 m wet to glass plates, using a four-way bar applicator. The flash-off time was 10 minutes. Dry film thicknesses after curing at 100 C. were approximately 40 m. The pendulum hardness was measured after 5-10 minutes. For all four polyester polyols in each of the three mixtures (9:1; 8:2; 7:3), the pendulum hardnesses over the entire cure time are higher than without polyester polyol (10:0). The more polyester polyol was used in the mixture, the higher the pendulum hardnesses.

TABLE-US-00003 TABLE 2 Formulations for the pendulum hardnesses of test series 1 (X/S = xylene/Solvenon PM. Nacure 2500 is 1% based on amino resin, solid/solid) Joncryl 504 Component NVF Reference Joncryl 504/B1 Joncryl 504/B2 [g] % 10:0 9:1 8:2 7:3 9:1 8:2 7:3 Joncryl 504 80.0 52.5 47.3 42.0 36.8 47.3 42.0 36.8 Luwipal 018 72.7 24.8 24.8 24.8 24.8 24.8 24.8 24.8 B1 75.0 5.6 11.2 16.8 B2 65.0 6.5 12.9 19.4 X/S = 7:3 22.8 22.3 22.0 21.6 21.4 20.3 19.0 Nacure 2500 25.0 0.72 0.72 0.72 0.72 0.72 0.72 0.72 NVF Joncryl 504/B3 Joncryl 504/B4 Component % 9:1 8:2 7:3 9:1 8:2 7:3 Joncryl 504 80.0 47.3 42.0 36.8 47.3 42.0 36.8 Luwipal 018 72.7 24.8 24.8 24.8 24.8 24.8 24.8 B3 70.0 6.0 12.0 18.0 B4 75.0 5.6 11.2 16.8 X/S = 7:3 21.9 21.2 20.4 22.3 22.0 21.6 Nacure 2500 25.0 0.72 0.72 0.72 0.72 0.72 0.72

TABLE-US-00004 TABLE 3 Pendulum hardnesses in swings for test series 1 Component 10 min 20 min 30 min 40 min 50 min 60 min Joncryl 504, 3 18 27 34 42 53 Reference Joncryl 8 29 39 48 54 68 504/B1 = 9:1 Joncryl 10 37 59 69 76 86 504/B1 = 8:2 Joncryl 17 50 73 83 90 99 504/B1 = 7:3 Joncryl 4 28 47 54 64 73 504/B2 = 9:1 Joncryl 14 44 64 73 80 88 504/B2 = 8:2 Joncryl 35 66 79 91 96 102 504/B2 = 7:3 Joncryl 3 23 40 50 57 66 504/B3 = 9:1 Joncryl 12 40 63 71 74 88 504/B3 = 8:2 Joncryl 25 63 81 88 93 100 504/B3 = 7:3 Joncryl 1 18 26 38 43 55 504/B4 = 9:1 Joncryl 1 19 32 42 50 60 504/B4 = 8:2 Joncryl 2 25 43 45 59 68 504/B4 = 7:3

[0211] Test Series 2: Film Properties Via the Temperature with Joncryl 504

[0212] Comparison of mixtures of polyacrylate-ol Joncryl 504/inventive polyesterols B1-B4 relative to polyacrylate-ol Joncryl 504 without inventive polyester polyol in development of pendulum hardness, Erichsen cupping, and crosslinking density in a 7:3 (solid/solid) polyols/Luwipal 018 system. The mixing ratios of Joncryl 504/polyester polyol were 9:1, 8:2, and 7:3 solid/solid. Films were applied at 150 m wet using a four-way bar applicator to a deep-drawn metal panel for the gradient oven. Curing took place after 10 minutes' flash-off in a temperature gradient of 80-180 C. for 20 minutes with storage overnight at (232) C. and (5010)% humidity. The dry film thicknesses were 40-50 m.

[0213] The pendulum hardnesses with branched polyester polyol are slightly to significantly better than without. They improve in line with the proportion of polyester polyol. With the formulations of B1, the Erichsen cupping is on average, unsystematically, somewhat poorer for the 90:10 mixture, significantly better for the 80:20 mixture, and comparable for the 70:30 mixture; in the case of B2 and B3, it is on average identical with the reference, and in the case of B4 it is significantly better. Looking at pendulum hardness and Erichsen cupping together, the polyester polyols of the invention are a gain. The crosslinking density in blends of all four polyester polyols is better than without.

TABLE-US-00005 TABLE 4 Joncryl 504/B1: Pendulum hardnesses and Erichsen cupping Pendulum hardness [swings] Joncryl Erichsen cupping [mm] T 504 J. [ C.] Reference 9:1 8:2 7:3 504 9:1 8:2 7:3 80 sticks sticks sticks sticks 10 10 10 10 89 sticks 3 4 13 10 10 10 10 100 17 27 34 42 10 10 10 9.8 109 50 66 70 81 9.4 8.9 10 9 120 90 95 103 104 7.4 7.2 9.2 7.5 132 109 112 118 123 5.5 4.5 7.7 5.9 143 115 115 122 129 3.2 3.3 5.7 3.5 157 119 121 124 130 1.9 1.8 3.2 2.3 168 123 130 129 133 1.7 0.4 1.7 1.7 180 125 133 135 136 1.3 0.7 2.5 1.2

TABLE-US-00006 TABLE 5 Joncryl 504/B2: Pendulum hardnesses and Erichsen cupping Pendulum hardness [swings] Joncryl Erichsen cupping [mm] T 504 J. [ C.] Reference 9:1 8:2 7:3 504 9:1 8:2 7:3 80 sticks sticks 1 10 10 10 10 10 89 sticks 1 13 16 10 10 10 10 100 17 22 49 77 10 10 9.8 9.9 109 50 46 94 90 9.4 9.2 8.4 9 120 90 92 114 118 7.4 7.7 7 7.7 132 109 108 120 127 5.5 6 4.9 6 143 115 118 122 129 3.2 4.6 3.5 3.1 157 119 121 123 129 1.9 2.6 2.7 2.4 168 123 136 125 139 1.7 1.7 1.2 1.2 180 125 131 129 143 1.3 1.8 0.9 1.3

TABLE-US-00007 TABLE 6 Joncryl 504/B3: Pendulum hardnesses and Erichsen cupping Pendulum hardness [swings] Joncryl Erichsen cupping [mm] T 504 J. [ C.] Reference 9:1 8:2 7:3 504 9:1 8:2 7:3 80 sticks sticks 1 2 10 10 10 10 89 sticks 2 11 14 10 10 10 10 100 17 20 30 43 10 10 9.6 9.7 109 50 51 69 85 9.4 8.9 8.8 8.7 120 90 98 100 117 7.4 7.1 7.5 7.3 132 109 113 109 125 5.5 5.5 5.6 5.6 143 115 118 116 128 3.2 3.5 4 4.1 157 119 123 121 131 1.9 2.2 1.9 2.2 168 123 126 127 134 1.7 1.7 1.7 1.4 180 125 128 129 140 1.3 1.7 1.5 1.3

TABLE-US-00008 TABLE 7 Joncryl 504/B4: Pendulum hardnesses and Erichsen cupping Pendulum hardness [swings] Joncryl Erichsen cupping [mm] T 504 J. [ C.] Reference 9:1 8:2 7:3 504 9:1 8:2 7:3 80 sticks sticks sticks sticks 10 10 10 10 89 sticks sticks sticks 3 10 10 10 10 100 17 17 19 25 10 10 10 10 109 50 53 56 61 9.4 9.3 9.9 9.6 120 90 95 96 103 7.4 7.3 8.2 8 132 109 110 104 107 5.5 5.9 7.2 6.6 143 115 119 120 122 3.2 3.3 4.4 4.3 157 119 123 122 126 1.9 2.6 3.4 2.4 168 123 126 127 128 1.7 1.7 2.1 2.2 180 125 129 134 135 1.3 2.6 1.5 2.5

TABLE-US-00009 TABLE 8 Joncryl 504/B1-B2 (top)/B3-B4 (bottom) Crosslinking density (xylene test) [ C.] Joncryl 504 Joncryl 504/B1 Joncryl 504/B2 Reference 9:1 8:2 7:3 9:1 8:2 7:3 50% 120 120 120 120 120 109 109 100% 143 132 132 132 132 120 120 Joncryl 504/B3 Joncryl 504/B4 9:1 8:2 7:3 9:1 8:2 7:3 50% 120 120 120 120 120 120 100% 132 120 120 132 132 120

[0214] Test Series 3: Chemical Resistance for Automobiles with Joncryl 504

[0215] Comparison of mixtures of polyacrylate-ol/inventive polyester polyol B3 relative to polyacrylate-ol Joncryl 504 without polyester polyol in chemical resistance. The coatings were cured at 140 C. for 20 minutes and for 16-24 hours at (232) C. and (5010)% humidity.

[0216] The greater the amount of polyester polyol used, the better the resistances. In its sulfuric acid resistance, the 8:2 mixture is poorer while being equal in the case of pancreatin and tree resin, and better by 3 C. for 5% aqueous sodium hydroxide than the reference, and hence, on average, is comparable. The 7:3 mixture is in accordance with the reference for sulfuric acid, the resistances otherwise being significantly better by 9 to 20 C. than the reference.

TABLE-US-00010 TABLE 9 Chemical resistances for automobiles ( C.) 1% 5% Tree H2SO4 NaOH Pancreatin resin Joncryl 504, Reference 45 55 50 30 Joncryl 504/B3 = 8:2 42 58 50 30 Joncryl 504/B3 = 7:3 45 64 63 50

[0217] Test Series 4:

[0218] Comparison of mixtures of polyester polyol/inventive polyester polyols B1, B3, B4 relative to polyester polyol without inventive polyester polyols in a coil coating application in a 4.4:1 (solid/solid) polyol/Luwipal 066 LF system. Luwipal 066 LF is an amino resin typically used in coil coating materials. The mixing ratios of polyester polyol/inventive polyester polyol were 7:3 solid/solid. Films were applied to 50 m wet with a wire doctor. Curing took place for 30 seconds in a coil oven at 300 C. (peak metal temperature 260 C.), with subsequent storage for 16-24 hours at (232) C. and (5010)% humidity. The dry film thickness was 20-22 m.

[0219] For the mixtures according to the invention, the crosslinking density (MEK double rubs) is better, the pencil hardness higher, the Erichsen cupping somewhat lower, and the impact and re-impact identical. All in all, therefore, the addition of the inventive polyester polyols produces an improvement in the film properties.

TABLE-US-00011 TABLE 10 Resin compositions and results of coil coating application NVF Raw materials [%] Reference B1 B3 B4 Dynapol LH 832-02 60 78.9 55.2 55.2 55.2 Luwipal 066 LF 95.6 10.3 10.3 10.3 10.3 B1 75 19.0 B3 70 20.3 B4 75 19 Nacure 2558 0.2 0.2 0.2 0.2 Butyl glycol 2.7 2.7 2.7 2.7 Solvesso 150 7.9 7.9 7.9 7.9 MEK [double rubs] <150 >200 >200 >200 Impact (4 pound) 160 160 160 160 [inch-pound] Re-Impact (4 pound) 160 160 160 160 [inch-pound] Erichsen [mm] 8.2 7.7 7.2 7.4 Pencil hardness 2H 3H 3H 3H