Aqueous dispersion and uses thereof

Abstract

The present invention relates to an aqueous dispersion comprising dispersed particles of an acrylic copolymer having a volume average particle size diameter (d50) of from 1 to 50 μm (microns), wherein the aqueous dispersion further comprises (i) an acrylic copolymer dispersant having an alkaline solubility higher than 50 wt. %, and being present in the dispersion in an amount of from 10 to 35% by weight, relative to the total amount of monomers used to prepare the acrylic copolymer of the dispersed polymeric particles; and (ii) decomposition products of an oil-soluble organic initiator.

Claims

1. An aqueous dispersion comprising: (i) dispersed particles of an acrylic copolymer having a volume average particle size diameter (d50) of from 1 to 50 μm (microns), (ii) from 10 to 35% by weight, relative to the total amount of monomers used to prepare the acrylic copolymer of the dispersed polymeric particles, of an acrylic copolymer dispersant having an alkaline solubility higher than 50 wt. %, and (iii) decomposition products of an oil-soluble organic initiator.

2. The aqueous dispersion according to claim 1, wherein the acrylic copolymer dispersant is at least partially neutralized and has: (a) an acid value of at least 40 mg KOH/g dispersion of acrylic copolymer dispersant, (b) a weight average molecular weight of least 30000 Daltons, and (c) a glass transition temperature from −50° C.

3. The aqueous dispersion as claimed in claim 1, wherein the alkaline solubility of the acrylic copolymer dispersant is higher than 70 wt. %.

4. The aqueous dispersion as claimed in claim 1, wherein the alkaline solubility of the acrylic copolymer dispersant is in a range which is higher than 50 wt. % and at most 90 wt. %.

5. The aqueous dispersion as claimed in claim 1, wherein the acid value of the dispersion of the acrylic copolymer dispersant is at least 50 mg KOH/g dispersion of acrylic copolymer dispersant and at most 100 mg KOH/g dispersion of acrylic copolymer dispersant.

6. The aqueous dispersion as claimed in claim 1, wherein the weight average molecular weight of the acrylic copolymer dispersant is at least 50000 Daltons and at most 1000000 Daltons.

7. The aqueous dispersion as claimed in claim 1, wherein the acrylic copolymer dispersant has a neutralization degree which is in a stoichiometric range from 80 to 120%.

8. The aqueous dispersion as claimed in claim 1, wherein the dispersion is storage-stable or semi-storage stable under standard conditions of relative humidity of 70% (±5%), ambient temperature of 23° C. (±2°), atmospheric pressure and an air flow of less than or equal to 0.1 m/s.

9. The aqueous dispersion as claimed in claim 1, wherein the amount of acrylic copolymer dispersant is at least 15% by weight, relative to the total amount of monomers used to prepare the acrylic copolymer of the dispersed polymeric particles.

10. The aqueous dispersion as claimed in claim 1, wherein the dispersed acrylic copolymer particles have a volume average particle size diameter (d50) of from 1 to 40 μm.

11. The aqueous dispersion as claimed in claim 1, wherein the dispersed acrylic copolymer particles have a volume average particle size diameter (d50) of from 2 to 25 μm.

12. The aqueous dispersion as claimed in claim 1, wherein the dispersed acrylic copolymer particles have a particle size distribution ((d90−d10)/d50) of at most 3.

13. The aqueous dispersion as claimed in claim 1, wherein the acrylic copolymer of the dispersed acrylic copolymer particles has a glass transition temperature Tg which is in a range from −50 to 150° C.

14. The aqueous dispersion as claimed in claim 1, wherein the acrylic copolymer of the acrylic copolymer dispersed particles comprises: a) from 0 to 10 wt. % of potentially ionic ethylenically mono-unsaturated monomers; b) from 0 to 10 wt. % of non-ionic ethylenically unsaturated monomers with a functional group for crosslinking; c) from 60 to 100 wt. % of non-ionic ethylenically mono-unsaturated monomers other than the monomers b); d) from 0 to 20 wt % of non-ionic ethylenically polyunsaturated monomer other than the monomers b); wherein the amount of the monomers of a) to d) sum to 100 wt. % and are relative to the total weight amount of the monomers to prepare the acrylic copolymer.

15. The aqueous dispersion as claimed in claim 14, wherein the non-ionic ethylenically mono-unsaturated monomers c) are selected from the group consisting of acrylonitrile, acrylates, methacrylates, itaconates, acrylamides, arylalkylenes and mixtures thereof.

16. The aqueous dispersion as claimed in claim 1, wherein the acrylic copolymer dispersant comprises: A) a (meth)acrylic acid monomer; and B) at least one monomer containing at least one acrylic or methacrylic moiety which is different than the (meth)acrylic acid monomer A).

17. The aqueous dispersion as claimed in claim 1, wherein the aqueous dispersion is a free-radical polymerisation product of ethylenically unsaturated monomers in the presence of the oil-soluble organic initiator and the acrylic copolymer dispersant.

18. The aqueous dispersion as claimed in claim 1, wherein the aqueous dispersion is free of non-aqueous solvent.

19. The aqueous dispersion as claimed in claim 1, wherein the dispersed acrylic copolymer particles have a density which is in a range from 0.95 to 1.10 g/ml.

20. The aqueous dispersion as claimed in claim 1, wherein the dispersion comprises solids in an amount from 30 to 65 wt. %.

21. A process for preparing the aqueous dispersion as claimed in claim 1, the process comprising the steps of: (A) preparing the acrylic copolymer dispersant by a process comprising the following steps: (A1) preparing a dispersion of acrylic copolymer by emulsion polymerisation of (meth)acrylic acid and at least one other monomer containing at least one acrylic or methacrylic moiety to obtain a dispersion of acrylic copolymer containing carboxylic acid groups and/or carboxylate salt groups; (A2) optionally filtering the dispersion obtained in step i) over a 75 micron filter in order to reduce the presence of sediment; and (A3) preparing an at least partially neutralized acrylic copolymer by neutralizing the acrylic copolymer containing carboxylic acid groups and/or carboxylate salt groups by reacting the acrylic copolymer containing carboxylic acid groups and/or carboxylate salt groups with a base in a stoichiometric amount of from 0.4 to 2.0; and (B) preparing the dispersed particles of acrylic copolymer by a process comprising the following steps: (B1) dissolving at least a part of the at least partially neutralized acrylic copolymer in water to obtain an at least partially neutralized acrylic copolymer solution (1); (B2) mixing ethylenically unsaturated monomers, wherein at least a part of the ethylenically unsaturated monomers contains a (meth)acrylic moiety, with an oil-soluble organic initiator to obtain an oil-soluble organic initiator solution (2) containing the ethylenically unsaturated monomers; (B3) transferring the solution (2) into the solution (1) to obtain a precursor composition; (B4) mixing the precursor composition of step (B3) to obtain a mixed composition; and (B5) conducting free-radical polymerisation of the mixed composition by increasing temperature of the mixed composition from 25 to 95° C. under atmospheric pressure until the dispersion contains 15 wt. % to about 65 wt. % solids.

22. An aqueous coating composition comprising the aqueous dispersion according to claim 1.

23. An aqueous coating composition comprising a blend of: (A) an aqueous first dispersion comprised of the aqueous dispersion according to claim 1; and (B) an aqueous second dispersion comprising dispersed polymeric particles of a latex polymer, wherein the polymeric particles of the latex polymer of the aqueous second dispersion have a volume average particle size diameter (d50) of less than 1 μm (micron) and wherein at least 90% of the polymer particles of the latex polymer of the second aqueous second dispersion, by weight of the total amount of the polymeric particles of the latex polymer, have a size less than 500 nm.

24. The aqueous coating composition as claimed in claim 23, wherein the second polymer is a vinyl polymer, a polyurethane, an alkyd polymer or a combination or mixture thereof.

25. The aqueous coating composition according to claim 23, wherein the aqueous second forms a film having a high gloss of greater than 60 gloss units at 60 degrees, and wherein (i) the weight ratio as calculated based on solid polymers, of the acrylic copolymer of the first dispersion to the latex polymer of the second dispersion is from 1/99 to 30/70; and (ii) the aqueous coating composition forms a matt coating exhibiting less than 40 gloss units at 60 degrees when applied to a substrate.

26. A method of forming a coated substrate comprising: (i) applying the aqueous coating composition according to claim 22 to a substrate; and (ii) drying the aqueous coating composition to obtain a matt coating, wherein the substrate is selected from the group consisting of natural leather, artificial leather, paper, foil, cardboard, wood, metal, concrete, fibres, tissues, plastic, and films.

Description

EXAMPLES 1-6: PREPARATION MICRON SIZED ACRYLIC COPOLYMER DISPERSIONS

(1) In a 2 liter glass 3-neck spherical reactor equipped with nitrogen inlet, Pt100, exhaust cooling and stirrer ingredients ‘1’ and ‘2’ (see tables below) are loaded to the reactor. Next ‘3’ is added and reactor content heated to 60° C. Upon reaching 60° C. ‘4’ is added to the reactor and content heated to 80-85° C. This temperature is maintained for 30 minutes to allow dispersant to dissolve.

(2) Next reactor content is cooled to room temperature.

(3) Ingredients ‘5’, ‘6’ and ‘7’ are loaded to a feed tank and mixed till ‘7’ is completely dissolved.

(4) Accordingly monomer feed tank content is at a set stirrer speed transferred to the reactor over a 45-60 minute period. After monomer has been transferred, feed vessel is rinsed with ‘8’ and dispersing hold at set agitator speed is maintained for a 30-minute period. Next reactor is heated to 40° C. and solution of ‘9’ in ‘10’ added to the reactor. This will trigger the polymerisation to start and temperature will rise to 70-90° C. After peak temperature has been obtained temperature is levelled at 80° C. for 60 minutes. After this hold, a solution of ‘11’ in ‘12’ is added to the reactor and 80° C. maintained for another 60 minutes. Next the final dispersion is cooled, unloaded and specified and the gloss of the coating is determined.

(5) In order to benefit from the dispersant activity of the acrylic copolymer dispersant prepared it was investigated how neutralization degree impacted processing and particle size control. To study this the neutralization degree was altered by changing the ammonia level (3′ and ‘4’) applied.

(6) Data and results are reported in below table.

(7) TABLE-US-00004 TABLE 3 Impact dispersant neutralisation on dispersion characteristics Label Ex-1 Ex-2 Ex-3 Ex-4 Ex-5 Ex-6  ‘1’ DM 455.92 455.92 455.92 455.92 455.92 455.92  ‘2’ Disp-1 239.96 239.96 239.96 239.96 239.96 239.96  ‘3’ Amm 4.23 6.34 8.44 10.91 13.09 15.27  ‘4’ Amm 4.23 6.34 8.44 10.91 13.09 15.27  ‘5’ BA 345.54 345.54 345.54 345.54 345.54 345.54  ‘6’ DPGDA 38.39 38.39 38.39 38.39 38.39 38.39  ‘7’ LPO 2.88 2.88 2.88 2.88 2.88 2.88  ‘8’ DM 60.65 56.73 52.53 47.59 43.23 38.87  ‘9’ SDT 0.96 0.96 0.96 0.96 0.96 0.96 ‘10’ DM 59.99 59.99 59.99 59.99 59.99 59.99 ‘11’ APS 0.96 0.96 0.96 0.96 0.96 0.96 ‘12’ DM 35.99 35.99 35.99 35.99 35.99 35.99 Total 1250.00 1250.00 1250.00 1250.00 1250.00 1250.00 Agitator speed [rpm] 450 450 450 450 450 450 Neutralisation degree [SA] 0.5 0.75 1.00 1.25 1.50 1.75 Dispersant on TM [wt %] 25.0 25.0 25.0 25.0 25.0 25.0 Tg calculated [° C.] −38 −38 −38 −38 −38 −38 Acid value - theor [mgKOH/g] 11.2 11.2 11.2 11.2 11.2 11.2 Appearance White White White White White White dispersion dispersion dispersion dispersion dispersion dispersion Storage stability Good Good Good Good Good Good Solids [wt %] 37.8 38.5 38.3 38.4 38.2 38.5 pH 7.0 7.3 7.7 8.1 8.4 8.7 Viscosity @25° C. [mPa .Math. s] 173 380 190 3620 41000 52000 d 50 [microns] 20.9 7.9 3.8 2.7 2.9 2.7 Span (d 90-d 10)/d 50 12.3 2.9 1.7 1.5 5.6 7.2 15 μm dry film LENETA chart Gloss @20° [GU] 0.5 0.2 0.3 1.2 1.7 1.7 Gloss @60° [GU] 5.0 2.8 3.4 10.7 13.9 15.6 Gloss @85° [GU] 6.4 8.7 25.1 53.0 28.6 40.1

EXAMPLES 7-10 AND COMPARATIVE EXPERIMENTS A-B

(8) Example 3 was repeated but with dispersants 2-6 as described above which were neutralized with a neutralization degree of 1.0 SA. These dispersants were evaluated on stabilisation performance and final particle size characteristics. Data and results are reported in below table.

(9) TABLE-US-00005 TABLE 4 Effect of dispersant modifications on final low Tg polymer dispersion characteristics Label Ex-7 Ex-8 Ex-9 Comp Ex A Comp Ex B Ex-10  ‘1’ DM 455.92 455.92 455.92 455.92 455.92 455.92  ‘2’ Disp-1 239.96 — — — — — Disp-2 — 239.96 — — — — Disp-3 — — 239.96 — — — Disp-4 — — — 239.96 — — Disp-5 — — — — 239.96 — Disp-6 — — — — — 239.96  ‘3’ Amm 8.44 8.44 8.44 8.44 8.44 8.44  ‘4’ Amm 8.44 8.44 8.44 8.44 8.44 8.44  ‘5’ BA 345.54 345.54 345.54 345.54 345.54 345.54  ‘6’ DPGDA 38.39 38.39 38.39 38.39 38.39 38.39  ‘7’ LPO 2.88 2.88 2.88 2.88 2.88 2.88  ‘8’ DM 52.53 52.53 52.53 52.53 52.53 52.53  ‘9’ SDT 0.96 0.96 0.96 0.96 0.96 0.96 ‘10’ DM 59.99 59.99 59.99 59.99 59.99 59.99 ‘11’ APS 0.96 0.96 0.96 0.96 0.96 0.96 ‘12’ DM 35.99 35.99 35.99 35.99 35.99 35.99 Total 1250.00 1250.00 1250.00 1250.00 1250.00 1250.00 Agitator speed [rpm] 450 350 350 350 350 650 Dispersant on TM [wt %] 25.0 25.0 25.0 25.0 25.0 25.0 Tg polymer calculated [° C.] −38 −38 −38 −38 −38 −38 Tg dispersant - DSC [° C.] 85 87 115 49 61 97 Acid value - theor [mgKOH/g] 11.2 11.2 11.2 3.7 7.3 14.6 Appearance White White White Beads Flocculates White dispersion dispersion dispersion formed upon dispersion processing Storage stability Good Good Good xxx xxx Good Solids [wt %] 38.3 34.8 32.3 xxx xxx 31.0 pH 7.7 8.7 7.7 xxx xxx 8.0 Viscosity @25° C. [mPa .Math. s] 190 33 580 xxx xxx 935 d 50 [microns] 3.8 6.2 1.0 113 xxx 2.1 Span (d 90-d 10)/d 50 1.7 7.9 1.1 1.4 xxx 2.3 15 μm dry film LENETA chart Gloss @20° [GU] 0.3 0.4 0.6 xxx xxx 0.7 Gloss @60° [GU] 3.4 3.9 13.9 xxx xxx 7.6 Gloss @85° [GU] 24.9 14.6 76.7 xxx xxx 39.9

COMPARATIVE EXPERIMENTS C AND D

(10) The effect of the hydrophilicity of the applied free radical initiator was studied using ammonium persulphate (APS) and tert-butyl hydroperoxide (t-BHPO) as free radical initiators. The data and results are reported in Table 5.

(11) TABLE-US-00006 TABLE 5 Label Comp Ex-C Comp Ex-D  ‘1’ DM 373.73 372.85  ‘2’ Disp-1 173.27 173.27  ‘3’ Amm 8.19 8.19  ‘4’ Amm 8.19 8.19  ‘5’ BA 249.51 249.51  ‘6’ DPGDA 27.72 27.72  ‘7a’ APS 2.08 —  ‘7b’ t-BHPO (70%) — 2.96  ‘7c’ t-BPEH — —  ‘7d’ MBPO (72.5%) — —  ‘7e’ AMBN — —  ‘8’ DM 86.63 86.63  ‘9’ SDT 0.69 0.69 ‘10’ DM 43.32 43.32 ‘11’ APS 0.69 0.69 ‘12’ DM 25.99 25.99 Total 1000.00 1000.00 Agitator speed [rpm] 350 350 Dispersant on TM [wt %] 25.0 25.0 Tg calculated [° C.] −38 −38 Appearance Coagulated Coagulated upon processing upon processing d50 [μm] Span (d90-d10)/d50 pH Storage stability Solids [wt %] Viscosity [mPa .Math. s] 15 μm dry film LENETA chart Gloss @20° [GU] Gloss @60° [GU] Gloss @85° [GU]

(12) From the results, it is clear that APS and t-BHPO have a negative impact on dispersion stability.

EXAMPLES 11-15

(13) The acrylic copolymeric dispersant 1 is used in different amounts and for different polymer composition. Data and results are reported in Table 6. As can be seen, the polymeric dispersant concentration applied allows particle size to be altered/controlled.

(14) TABLE-US-00007 TABLE 6 Label Ex-11 Ex-12 Ex-13 Ex-14 Ex-15  ‘1’ DM 585.86 639.90 585.86 431.02 573.72  ‘2’ Disp-1 201.52 151.14 201.52 171.72 151.14  ‘3’ Amm 7.33 5.49 7.33 6.23 5.50  ‘4’ Amm 7.33 5.49 7.33 6.23 5.50  ‘5a’ MMA 322.43 322.43 — — —  ‘5b’ BMA — — 290.18 329.01 290.19  ‘6’ DPGDA — — 32.24 36.55 32.24  ‘7’ LPO 2.42 2.42 2.42 1.83 2.42  ‘8’ DM 41.51 41.51 41.51 247.01 148.19  ‘9’ APS 0.81 0.81 0.81 0.92 0.81 ‘10’ DM 80.79 80.79 80.79 17.47 40.30 Total 1250.00 1250.00 1250.00 1250.00 1250.00 Agitator speed [rpm] 350 300 350 250 250 Dispersant on TM [wt %] 25.0 18.75 25.0 15.8 15.8 Tg calculated [° C.] 105 105 28 28 28 Appearance White White White White White dispersion dispersion dispersion dispersion dispersion Storage stability Good Good Good Good Good d 50 [μm] 9.2 20.7 12.1 17.7 33.0 Span (d 90-d 10)/d 50 2.1 2.1 1.9 1.8 1.8 pH 7.9 8.2 8.0 8.4 8.4 Solids [wt %] 32.5 30.0 32.1 34.2 30.6 Viscosity [mPa .Math. s] 850 300 90 50 25 15 μm dry film LENETA chart Gloss @20° [GU] 2.4 1.3 0.3 1.4 1.3 Gloss @60° [GU] 7.6 3.8 2.3 3.2 3.6 Gloss @85° [GU] 2.4 0.8 1.9 1.3 1.8

(15) Results clearly shows the impact of the dispersant concentration on particle size. The dispersant is universal in the sense that similar particle size trends can be obtained with different polymeric phase compositions.