SOLUTION OF POLYPHENOLS IN AMINE

Abstract

A solution including 5 to 65 wt. % polyphenols which are solid at room temperature and 35 to 95 wt. % amines of formula (I). The solution is preferably used for preparing a curing agent for epoxy resins. The solution has low viscosity and can be readily mixed with, and is compatible with, epoxy resins. The solution allows in particular readily processable, low-emission epoxy resin coatings having rapid curing, high final hardness, a flawless, glossy surface and low levels of yellowing, which also cure in a problem-free manner in cold conditions to form coatings of high quality and robustness without using any, or using only a small amount of, thinners.

Claims

1. A solution comprising 5% to 65% by weight of room temperature solid polyphenols and 35% to 95% by weight of amines of the formula (I) ##STR00008## where A is a linear or branched alkylene radical having 2 to 10 carbon atoms and R is a monovalent hydrocarbon radical optionally containing an oxygen atom and having 1 to 12 carbon atoms, where the amine of the formula (I) has a total of 8 to 15 carbon atoms and the two nitrogen atoms are separated from one another by at least two carbon atoms.

2. The solution as claimed in claim 1, wherein the room temperature solid polyphenol is selected from the group consisting of gallic acid, diphenolic acid, resveratrol, catechin and polymers containing phenol groups.

3. The solution as claimed in claim 1, wherein the room temperature solid polyphenol is a phenolic resin of the formula (II) ##STR00009## where n has an average value of 1 to 45, and R.sup.1 is independently H or an aliphatic hydrocarbon radical having 1 to 15 carbon atoms.

4. The solution as claimed in claim 1, wherein A is selected from 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,3-butylene, 2-methyl-1,2-propylene, 1,3-pentylene, 1,5-pentylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene, 2-methyl-1,5-pentylene, 1,7-heptylene, 1,8-octylene, 2,5-dimethyl-1,6-hexylene, 1,9-nonylene and 1,10-decylene.

5. The solution as claimed in claim 1, wherein R contains at least one aromatic or aliphatic ring and is selected from benzyl, furfuryl, 2-phenylethyl, cyclohexylmethyl and tetrahydrofurfuryl.

6. The solution as claimed in claim 1, wherein it includes 5% to 65% by weight of room temperature solid polyphenols, 35% to 95% by weight of amines of the formula (I), and 0% to 30% by weight of further amines that do not conform to the formula (I) and/or thinners and/or further accelerators.

7. The solution as claimed in claim 6, wherein it additionally includes at least one amine of the formula (Ia) and/or one amine of the formula (Ib) ##STR00010## where A and R are each the same radical as in the corresponding amine of the formula (I), and/or amine-functional adducts of the amine of the formula (I) with at least one mono- or polyepoxide.

8. The solution as claimed in claim 1, wherein the viscosity at 20 C. measured by cone-plate viscometer is in the range from 0.01 to 100 Pa.Math.s.

9. A curing agent for epoxy resins, comprising the solution as claimed in claim 1 and at least one further amine having at least three amine hydrogens.

10. The curing agent as claimed in claim 9, wherein the further amine having at least three amine hydrogens is selected from the group consisting of amines of the formula (I), 1,5-diamino-2-methylpentane, 2-butyl-2-ethylpentane-1,5-diamine, 2,2 (4),4-trimethylhexane-1,6-diamine, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl) methane, isophoronediamine, 2 (4)-methyl-1,3-diaminocyclohexane, 2,5 (2,6)-bis(aminomethyl) bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)benzene, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, N-(2-aminoethyl) propane-1,3-diamine, N,N-bis(3-aminopropyl)ethylenediamine, bis(hexamethylene)triamine, polyoxypropylenediamines having an average molecular weight M.sub.n in the range from 200 to 500 g/mol, polyoxypropylenetriamines having an average molecular weight M.sub.n in the range from 300 to 500 g/mol, 3-(3-(dimethylamino) propylamino) propylamine, 2,5-bis(aminomethyl) furan, 2,5-bis(aminomethyl)tetrahydrofuran, bis(5-aminomethylfuran-2-yl) methane, bis(5-aminomethyltetrahydrofuran-2-yl) methane, 2,2-bis(5-aminomethylfuran-2-yl) propane, 2,2-bis(5-aminomethyltetrahydrofuran-2-yl) propane, amine-functional adducts of the amines mentioned with mono- or polyepoxides, phenalkamines and mixtures of two or more of the amines mentioned.

11. The curing agent as claimed in claim 9, wherein the curing agent contains 2% to 30% by weight of room temperature solid polyphenols based on the sum total of all liquid or dissolved constituents present in the curing agent.

12. The curing agent as claimed in claim 9, wherein the curing agent, based on the sum total of all liquid or dissolved constituents present in the curing agent, has an amine hydrogen equivalent weight of 50 to 140 g/eq.

13. The curing agent as claimed in claim 9, wherein the curing agent, based on the sum total of all liquid or dissolved constituents present in the curing agent, has a viscosity at 20 C. measured by cone-plate viscometer is in the range from 10 to 5,000 mPa.Math.s.

14. An epoxy resin composition comprising a resin component containing at least one epoxy resin and either a curing agent component comprising the curing agent as described in claim 9 or a curing agent component comprising at least one amine having at least three amine hydrogens and, as a separate, third component, the solution comprising 5% to 65% by weight of room temperature solid polyphenols and 35% to 95% by weight of amines of formula (I).

15. A cured epoxy resin composition obtained from the epoxy resin composition as claimed in claim 14 after mixing the components.

Description

EXAMPLES

[0190] Working examples are adduced hereinafter, which are intended to further elucidate the invention described. It will be apparent that the invention is not limited to these described working examples.

[0191] AHEW stands for amine hydrogen equivalent weight.

[0192] EEW stands for epoxy equivalent weight.

[0193] Standard climatic conditions (SCC) refers to a temperature of 231 C. and a relative air humidity of 505%.

[0194] The chemicals used were from Sigma-Aldrich Chemie GmbH, unless otherwise stated.

Substances and Abbreviations Used:

[0195] Araldite GY 250: bisphenol A diglycidyl ether, EEW about 187 g/eq (Huntsman) [0196] Araldite DY-E: monoglycidyl ethers of C.sub.12 to C.sub.14 alcohols, EEW about 290 g/eq (Huntsman) [0197] Araldite DY-H: hexanediol diglycidyl ether, EEW about 147 g/eq (from Huntsman) [0198] B-EDA: N-benzylethane-1,2-diamine, 150.2 g/mol, AHEW 50.1 g/eq, prepared as described hereinafter [0199] B-EDA mix: reaction mixture containing N-benzylethane-1,2-diamine and N,N-dibenzylethane-1,2-diamine in a weight ratio of 85/15, prepared as described hereinafter, AHEW 55 g/eq [0200] F-EDA: N-furfurylethane-1,2-diamine, 140.1 g/mol, AHEW 46.7 g/eq, prepared as described hereinafter [0201] B-PDA: N-benzylpropane-1,2-diamine, 164.4 g/mol, AHEW 54.8 g/eq, prepared as described hereinafter [0202] DMAPAPA: 3-(3-dimethylaminopropylamino) propylamine, AHEW 53 g/eq (DMAPAPA, from Arkema) [0203] IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6 g/eq (Vestamin IPD, Evonik) [0204] MXDA: 1,3-bis(aminomethyl)benzene, AHEW 34 g/eq (Mitsubishi Gas Chemical) [0205] BAC 1,3-bis(aminomethyl)cyclohexane, AHEW 35.5 g/eq (from Mitsubishi Gas Chemical) [0206] Phenolic resin PH-1 phenol-formaldehyde novolak, average molecular weight M.sub.n about 430 g/mol, softening point 65 to 75 C. (Alnovol PN 327/100, from Allnex) [0207] Phenolic resin PH-2 phenol-formaldehyde novolak, average molecular weight M.sub.n about 440 g/mol, softening point 65 to 75 C. (Supraplast) 3616, from Sd-West-Chemie) [0208] Phenolic resin PH-3 phenol-formaldehyde novolak, average molecular weight M.sub.n about 950 g/mol, softening point 78 to 82 C. (Phenolite TD-2131, from DIC) [0209] Phenolic resin PH-4 phenol-formaldehyde novolak, average molecular weight M.sub.n about 2,400 g/mol, softening point 108 to 120 C. (Alnovol PN 320, from Allnex) [0210] Phenolic resin PH-5 phenol-formaldehyde novolak, average molecular weight M.sub.n about 2,600 g/mol, softening point 95 to 110 C. (FERS FB8000SH, from Sumimoto Bakelite) [0211] DPA diphenolic acid (4,4-bis(4-hydroxyphenyl) valeric acid) [0212] K54 2,4,6-tris(dimethylaminomethyl) phenol (Ancamine K54, from Evonik)

Reaction Mixture Containing N-Benzylethane-1,2-Diamine (B-EDA Mix)

[0213] An initial charge of 180.3 g (3 mol) of ethane-1,2-diamine at room temperature was mixed with a solution of 106.0 g (1 mol) of benzaldehyde in 1,200 ml of isopropanol, and hydrogenated at 80 C., hydrogen pressure 80 bar and an H.sub.2 flow rate of 5 ml/min in a continuous hydrogenation apparatus with a Pd/C fixed bed catalyst, and the hydrogenated solution was freed of the volatile constituents on a rotary evaporator at 65 C. This afforded a yellowish clear liquid having a content, determined by GC, of N-benzylethane-1,2-diamine of about 81% by weight and of N,N-dibenzylethane-1,2-diamine of about 14% by weight, a content of ethane-1,2-diamine of 0.3% by weight and a calculated AHEW of 55 g/eq, which was used hereinafter as B-EDA mix.

N-Benzylethane-1,2-diamine (B-EDA)

[0214] A portion of the reaction mixture containing N-benzylethane-1,2-diamine (B-EDA mix), prepared as described above, was purified at 80 C. by distillation under reduced pressure. This afforded a colorless liquid having an AHEW of 50.1 g/eq and a content, determined by GC, of N-benzylethane-1,2-diamine of >97%, which was used hereinafter as B-EDA.

N-Furfurylethane-1,2-diamine (F-EDA)

[0215] An initial charge of 105.2 g (1.75 mol) of ethane-1,2-diamine at room temperature was mixed with a solution of 48.1 g (0.5 mol) of furfural in 1,200 ml of isopropanol, and hydrogenated at 80 C., hydrogen pressure 80 bar and an H.sub.2 flow rate of 5 ml/min in a continuous hydrogenation apparatus with a Pd/C fixed bed catalyst, and the hydrogenated solution was freed of the volatile constituents on a rotary evaporator at 65 C. The resulting reaction mixture was purified by distillation at 70 C. under reduced pressure. This afforded a colorless liquid having an AHEW of 46.7 g/eq and a content, determined by GC, of N-furfurylethane-1,2-diamine of 94.6% by weight and of N-tetrahydrofurfurylethane-1,2-diamine of 5.3% by weight, which was used hereinafter as F-EDA.

N-Benzylpropane-1,2-diamine (B-PDA)

[0216] An initial charge of 222.4 g (3 mol) of propane-1,2-diamine at room temperature was mixed with a solution of 106.0 g (1 mol) of benzaldehyde in 1,200 ml of isopropanol, and hydrogenated at 80 C., hydrogen pressure 80 bar and an H.sub.2 flow rate of 5 ml/min in a continuous hydrogenation apparatus with a Pd/C fixed bed catalyst, and the hydrogenated solution was freed of the volatile constituents on a rotary evaporator at 65 C. The resulting reaction mixture was purified by distillation at 80 C. under reduced pressure. This afforded a colorless liquid having an AHEW of 54.8 g/eq and a content, determined by GC, of N-benzylpropane-1,2-diamine of >97% by weight and, by .sup.1H NMR, a ratio of N.sup.1-benzylpropane-1,2-diamine and N.sup.2-benzylpropane-1,2-diamine of about 2/1, which was used hereinafter as B-PDA.

Preparation of Solutions:

Solutions L-1 to L-28:

[0217] According to tables 1 and 2, for each solution, an initial charge of the specified amine was heated up to 50 to 80 C., the specified polyphenol in the specified amount was dissolved in the amine while stirring, and the solution was cooled down to room temperature.

[0218] After a storage time of the solution of 24 hours at room temperature, the viscosity of the solution was measured on a thermostatted Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1, cone tip-plate distance 0.05 mm) at the specified temperature, using a shear rate of 100 s.sup.1 for viscosities of less than 100 mPa.Math.s and a shear rate of 10 s.sup.1 for viscosities of 100 mPa.Math.s or more.

[0219] The solutions labeled (Ref.) are noninventive comparative examples.

TABLE-US-00001 TABLE 1 Composition and viscosity of solutions L-1 to L-22. Phenolic Weight Viscosity Amine resin ratio.sup.1 [mPa .Math. s] Solution L-1 B-EDA PH-1 80/20 89 (20 C.) Solution L-2 B-EDA PH-1 70/30 525 (20 C.) Solution L-3 B-EDA PH-1 60/40 7,920 (20 C.) Solution L-4 F-EDA PH-1 80/20 68 (20 C.) Solution L-5 F-EDA PH-1 70/30 315 (20 C.) Solution L-6 F-EDA PH-1 60/40 3,710 (20 C.) Solution L-7 B-PDA PH-1 80/20 94 (20 C.) Solution L-8 (Ref.) IPDA PH-1 80/20 2,022 (20 C.) Solution L-9 (Ref.) IPDA PH-1 70/30 38,700 (25 C.) Solution L-10 MXDA PH-1 80/20 85 (20 C.) (Ref.) Solution L-11 MXDA PH-1 70/30 695 (20 C.) (Ref.) Solution L-12 MXDA PH-1 60/40 14,900 (20 C.) (Ref.) Solution L-13 BAC PH-1 80/20 153 (20 C.) (Ref.) Solution L-14 BAC PH-1 70/30 1,830 (20 C.) (Ref.) Solution L-15 BAC PH-1 60/40 28,900 (25 C.) (Ref.) Solution L-16 TMD PH-1 80/20 83 (20 C.) (Ref.) Solution L-17 TMD PH-1 70/30 565 (20 C.) (Ref.) Solution L-18 TMD PH-1 60/40 9,590 (20 C.) (Ref.) Solution L-19 B-EDA PH-2 80/20 78 (20 C.) Solution L-20 B-EDA PH-3 80/20 114 (20 C.) Solution L-21 B-EDA PH-4 80/20 186 (20 C.) Solution L-22 B-EDA PH-5 80/20 156 (20 C.) .sup.1weight ratio of amine/phenolic resin

TABLE-US-00002 TABLE 2 Composition and viscosity of solutions L-23 to L-28. Weight Viscosity Amine Polyphenol ratio.sup.1 [mPa .Math. s] Solution L-23 B-EDA DPA 80/20 330 (20 C.) Solution L-24 B-EDA DPA 70/30 8,860 (20 C.) Solution L-25 B-EDA mix DPA 80/20 590 (20 C.) Solution L-26 IPDA DPA 80/20 too thick (paste) (Ref.) Solution L-27 MXDA DPA 80/20 350 (20 C.) (Ref.) Solution L-28 BAC DPA 80/20 960 (20 C.) (Ref.) .sup.1weight ratio of amine/polyphenol
Production of curing agents for epoxy resins:

Curing Agents H-1 to H-19:

[0220] For each curing agent, the ingredients specified in table 3 in the specified amounts (in parts by weight) were mixed using a centrifugal mixer (SpeedMixer DAC 150, FlackTek Inc.) and stored with exclusion of moisture.

[0221] The viscosity of the curing agents was measured as described above.

[0222] The amine equivalent weight (AHEW) of the curing agents was calculated.

[0223] The results are reported in table 3.

[0224] Curing agents labeled (Ref.) are noninventive comparative examples.

TABLE-US-00003 TABLE 3 Composition (in % by weight) and properties of curing agents H-1 to H-19. Further Viscosity AHEW Solution ingredients [mPa .Math. s] [g/eq] Curing agent H-1 (Ref.) 100% B-EDA 7 50.1 Curing agent H-2 55.5% L-1 44.5% B-EDA 26 56.4 Curing agent H-3 100% L-1 89 62.6 Curing agent H-4 55.5% L-19 44.5% B-EDA 20 56.4 Curing agent H-5 55.5% L-21 44.5% B-EDA 25 56.4 Curing agent H-6 55.5% L-22 44.5% B-EDA 32 56.4 Curing agent H-7 (Ref.) 92.6% B-EDA n.d. 54.1 7.4% K54 Curing agent H-8 (Ref.) 100% F-EDA 3 46.7 Curing agent H-9 59.1% L-4 40.9% F-EDA 21 53.0 Curing agent H-10 51.2% L-7 48.8% B-PDA 22 61.1 Curing agent H-11 55.0% L-1 30.9% B-EDA 20 56.9 14.1% DMAPAPA Curing agent H-12 (Ref.) 64.0% L-8 36.0% IPDA 233 48.9 Curing agent H-13 (Ref.) 77.7% L-10 22.3% MXDA 47 40.3 Curing agent H-14 (Ref.) 74.9% L-13 25.1% BAC 79 41.8 Curing agent H-15 (Ref.) 68.2% L-16 31.8% TMD 30 45.9 Curing agent H-16 55.5% L-23 44.5% B-EDA 48 56.4 Curing agent H-17 51.1% L-25 48.9% B-EDA mix 49 61.3 Curing agent H-18 (Ref.) 77.7% L-27 22.3% MXDA 111 40.3 Curing agent H-19 (Ref.) 74.9% L-28 25.1% BAC 230 41.8 n.d. stands for not determined

Production of Epoxy Resin Compositions:

Compositions Z-1 to Z-19:

[0225] For each composition, the ingredients of the resin component reported in tables 4 to 7 were mixed in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer DAC 150, FlackTek Inc.) and stored with exclusion of moisture.

[0226] Subsequently, the curing agents specified in tables 4 to 7, in the specified amounts (in parts by weight), were mixed with the resin component using the centrifugal mixer, and the mixed composition was immediately tested as follows:

[0227] Viscosity (5) was measured as described above at a temperature of 20 C. 5 min after the resin component and the curing agent component had been mixed.

[0228] Gel time was determined by moving a freshly mixed amount of about 3 g under standard climatic conditions with a spatula at regular intervals until the mass underwent gelation.

[0229] Shore D hardness was determined in accordance with DIN 53505 on two cylindrical test specimens (diameter 20 mm, thickness 5 mm), one of which was stored under standard climatic conditions and the other at 8 C. and 80% relative humidity, and the hardness measured in each case after 1 day (24 h) and after 2 days.

[0230] In addition, a film was applied to a glass plate in a layer thickness of 500 m, and this was stored/cured under standard climatic conditions. Knig's hardness (Knig's pendulum hardness to DIN EN ISO 1522) was determined on this film after 1 day, 2 days, 7 days and 14 days (1d SCC), (2d SCC), (7d SCC), (14d SCC). After 14 days, the appearance (SCC) of the film was assessed. A clear film was described as attractive if it had a glossy and nonsticky surface with no structure. Structure referred to any kind of marking or pattern on the surface.

[0231] A further film was applied to a glass plate in a layer thickness of 500 m and, immediately after application, stored/cured at 8 C. and 80% relative humidity for 7 days and then under standard climatic conditions for 2 weeks. 24 hours after application, a polypropylene bottletop beneath which a moist sponge had been positioned was placed on the film. After a further 24 hours, the sponge and the bottletop were removed and positioned at a new point on the film, from which they were in turn removed and repositioned after 24 hours, which was done 4 times in total. The appearance of this film was then assessed (designated Appearance (8/80%) in the tables) in the same way as described for Appearance (SCC). Also reported in each case here was the number and nature of visible marks that had formed in the film as a result of the damp sponge or the bottletop on top. The number of white discolored spots was reported as blushing. (1) denoted one faint white discolored spot. 1 denoted one clear white discolored spot. Ring was used to state how many ring-shaped impressions were present as a result of indentation of the bottletop placed on. (1) denoted a faint impression of the bottletop, 1 a clear impression. (A ring-shaped impression indicates that the coating was not yet ready to be walked on.) Knig's hardness was again determined on the films thus cured, in each case after 7 days at 8 C. and 80% relative humidity (Knig's hardness (7d 8/80%)) and then after a further 2 days under SCC (Knig's hardness (+2d SCC)), 7 days under SCC (Knig's hardness (+7d SCC)), and 14 days under SCC (Knig's hardness (+14d SCC)). As a measure of yellowing, the change in color after stressing in a weathering tester was also determined. For this purpose, a further film was applied to a glass plate in a layer thickness of 500 m and this was stored/cured under standard climatic conditions for 2 weeks and then stressed for 72 hours at a temperature of 65 C. in a Q-Sun Xenon Xe-1 weathering tester having a Q-SUN Daylight-Q optical filter and a xenon lamp having a light intensity of 0.51 W/m.sup.2 at 340 nm (Q-Sun (72 h)). The color difference E of the stressed film versus the corresponding unstressed film was then determined using an NH310 colorimeter from Shenzen 3NH Technology Co. LTD equipped with silicon photoelectric diode detector, light source A, color space measurement interface CIE L*a*b*C*H*. E values up to 5 represent slight yellowing.

[0232] The results are given in tables 4 to 7.

[0233] The compositions labeled (Ref.) are noninventive comparative examples.

TABLE-US-00004 TABLE 4 Composition and properties of Z-1 to Z-7. Composition Z-1 Z-7 Resin component: (Ref.) Z-2 Z-3 Z-4 Z-5 Z-6 (Ref.) Araldite GY-250 167.2 167.2 167.2 167.2 167.2 167.2 167.2 Araldite DY-E 31.8 31.8 31.8 31.8 31.8 31.8 31.8 H-1 H-2 H-3 H-4 H-5 H-6 H-7 Curing agent: 50.1 56.4 62.6 56.4 56.4 56.4 54.1 Viscosity (5) [mPa .Math. s] 190 390 740 460 590 510 230 Gel time (h:min) 5:20 3:15 2:30 2:55 3:00 2:50 4:30 Shore D (1 d SCC) 61 79 75 68 73 71 74 (2 d SCC) 62 81 77 78 75 77 75 Shore D (1 d 8/80%) n.m..sup.1 70 73 66 62 65 19 (2 d 8/80%) 72 73 75 73 70 74 76 Knig's hardness(1 d S 56 129 139 102 120 109 106 [s] (2 d SCC) 72 162 161 137 158 129 149 (7 d SCC) 136 181 182 182 181 179 184 (14 d SCC) 151 200 198 200 201 200 201 Appearance (SCC) attractive attractive attractive attractive attractive attractive attractive Q-Sun (72 h) E 4.2 8.6 10.7 8.5 11.7 7.0 12.3 Knig's hardness (7 d 8 21 56 71 35 49 42 49 [s] (+2 d SCC) 55 130 161 69 134 120 106 (+7 d SCC) 85 176 176 154 171 150 136 (+14 d SCC) 112 182 184 168 175 169 148 Appearance (8/80%) attractive attractive attractive attractive attractive attractive attractive Blushing none none none none none none 1 Ring none none none none none none none KH (cold)/KH (SCC) .sup.2 74% 91% 93% 84% 87% 85% 74% .sup.1not measurable (too soft) .sup.2 Knig's hardness (7 d 8/80% + 14 d SCC) relative to Konig's hardness (14 d SCC) in percent indicates data missing or illegible when filed

TABLE-US-00005 TABLE 5 Composition and properties of Z-8 to Z-11. Composition Z-8 Resin component: (Ref.) Z-9 Z-10 Z-11 Araldite GY-250 167.2 167.2 167.2 167.2 Araldite DY-E 31.8 31.8 31.8 31.8 H-8 H-9 H-10 H-11 Curing agent: 46.7 53.0 61.1 56.9 Knig's hardness(1 d S 38 105 115 101 [s] (2 d SCC) 57 129 171 113 (7 d SCC) 118 162 203 186 (14 d SCC) 119 182 205 201 Appearance (SCC) attractive attractive attractive attractive Q-Sun (72 h) E 12.9 29.0 3.9 17.2 Knig's hardness (7 d 8 11 27 66 60 [s] (+2 d SCC) 36 64 175 115 (+7 d SCC) 52 137 201 157 (+14 d SCC) 81 154 201 174 Appearance (8/80%) attractive attractive attractive attractive Blushing 1 (1) none (1) Ring 1 none (1) none KH (cold)/KH (SCC) .sup.1 68% 85% 98% 87% .sup.1 Knig's hardness (7 d 8/80% + 14 d SCC) relative to Knig's hardness (14 d SCC) in percent indicates data missing or illegible when filed

TABLE-US-00006 TABLE 6 Composition and properties of Z-12 to Z-15. Composition Z-12 Z-13 Z-14 Z-15 Resin component: (Ref.) (Ref.) (Ref.) (Ref.) Araldite GY-250 167.2 167.2 167.2 167.2 Araldite DY-E 31.8 31.8 31.8 31.8 H-12 H-13 H-14 H-15 Curing agent: 48.9 40.3 41.8 45.9 Viscosity (5) [mPa .Math. s] 1,240 760 890 620 Gel time (h:min) 2:45 2:15 1:35 2:20 Shore D (1 d SCC) 65 75 76 76 (2 d SCC) 72 79 81 83 Shore D (1 d 8/80%) 45 78 73 34 (2 d 8/80%) 54 81 77 72 Knig's hardness(1 d S 132 73 113 63 [s] (2 d SCC) 158 94 87 99 (7 d SCC) 195 101 95 129 (14 d SCC) 201 125 105 197 Appearance (SCC) structure structure structure structure Q-Sun (72 h) E 7.9 11.4 14.0 16.1 Knig's hardness (7 d 8 67 18 35 11 [s] (+2 d SCC) 70 34 36 14 (+7 d SCC) 137 43 38 29 (+14 d SCC) 141 63 42 43 Appearance (8/80%) hazy hazy structure hazy Blushing 4 3 2 3 Ring none none none none KH (cold)/KH (SCC) .sup.1 70% 50% 40% 22% .sup.1 Knig's hardness (7 d 8/80% + 14 d SCC) relative to Knig's hardness (14 d SCC) in percent indicates data missing or illegible when filed

TABLE-US-00007 TABLE 7 Composition and properties of Z-16 to Z-19. Composition Z-18 Z-19 Resin component: Z-16 Z-17 (Ref.) (Ref.) Araldite GY-250 167.2 167.2 167.2 167.2 Araldite DY-E 31.8 31.8 31.8 31.8 H-16 H-17 H-18 H-19 Curing agent: 56.4 61.3 40.3 41.8 Viscosity (5) [mPa .Math. s] 520 510 n.m..sup.1 n.m..sup.1 Gel time (h:min) 3:20 3:25 n.m..sup.1 n.m..sup.1 Shore D (1 d SCC) 79 78 n.m..sup.1 n.m..sup.1 (2 d SCC) 80 80 Shore D (1 d 8/80) 61 62 n.m..sup.1 n.m..sup.1 (2 d 8/80) 63 74 Knig's hardness(1 d S 129 99 n.m..sup.1 n.m..sup.1 [s] (2 d SCC) 167 168 (7 d SCC) 200 185 (14 d SCC) 202 195 Appearance (SCC) attractive attractive n.m..sup.1 n.m..sup.1 Knig's hardness (7 d 8 57 56 n.m..sup.1 n.m..sup.1 [s] (+2 d SCC) 126 143 (+7 d SCC) 181 185 (+14 d SCC) 185 192 Appearance (8/80%) attractive attractive n.m..sup.1 n.m..sup.1 Blushing (1) (1) Ring none none KH (cold)/KH (SCC) .sup.2 91% 98% n.m..sup.1 n.m..sup.1 .sup.1not measurable: inhomogeneous on mixing owing to incompatibility of the curing agent with the resin component .sup.2 Knig's hardness (7 d 8/80% + 14 d SCC) relative to Knig's hardness (14 d SCC) in percent indicates data missing or illegible when filed

Use of a Polyphenol Solution as a Separate Component:

Compositions Z-20 to Z-22:

[0234] For these compositions, the resin component specified in table 8 in the specified amount (in parts by weight) was used as the first component.

[0235] In addition, the curing agent component specified in table 8 in the specified amounts (in parts by weight) was used as the second component.

[0236] A further third component used was the solution specified in table 8 in the specified amounts (in parts by weight).

[0237] The components of each composition were processed using a centrifugal mixer to give a homogeneous liquid, and this was tested immediately as follows:

[0238] Viscosity, gel time and Shore D were tested as described for composition Z-1. Moreover, a film was applied to a glass plate in a layer thickness of 500 m and stored at 8 C. and 80% relative humidity for 7 days. 24 hours after application, a polypropylene bottletop was placed onto the film, beneath which a moist sponge had been positioned. After a further 24 hours, the sponge and the bottletop were removed and positioned at a new point on the film, from which they were in turn removed and repositioned after 24 hours, which was done 4 times in total. Subsequently, the appearance of the film was assessed as described for composition Z-1 Appearance (8/80%).

[0239] The results are reported in table 8.

[0240] The composition labeled (Ref.) is a comparative example.

TABLE-US-00008 TABLE 8 Composition and properties of Z-20 to Z-22. Composition Z-20 (Ref.) Z-21 Z-22 Resin component (first comp.): Sikafloor-264N (A) (RAL 5005) .sup.1 436.0 436.0 436.0 Curing agent component (second comp.): Sikafloor-264N (B) .sup.2 120.0 108.0 96.0 Solution L-3 (third component) 8.2 16.4 Viscosity (5) [Pa .Math. s] 2.5 3.2 4.9 Gel time (h:min) 2:55 2:25 2:05 Shore D (1 d SCC) 45 51 58 (2 d SCC) 60 67 69 Shore D (1 d 8/80%) 33 41 53 (2 d 8/80%) 57 65 67 Appearance (8/80%) attractive attractive attractive Blushing 2 1 1 Ring none none none .sup.1 filled pigmented resin component with an epoxy resin floor coating, EEW 436 g/eq (from Sika) .sup.2 formulated unfilled curing agent for epoxy resins, AHEW 120 g/eq (from Sika)