METHOD FOR PREPARING WATER-BASED AEROSOL PAINT COMPOSITION AND THE USAGE OF PAINT MATERIAL

Abstract

The invention relates to a method for testing a mutual combability of coating material and propellant and preparing a water based aerosol paint composition having a high concentration of coating material said method comprising: selecting at least one pair of polymeric resin and propellant, further selecting said selected propellant-polymeric resin-pair so that the propellant and the polymeric resin will pass the mutual combability test in a pressurized vessel in the presence of water-based solvent, providing into an aerosol can A) 50-85% w/w of coating material, and B) selected propellant 15-50% w/w; and sealing the can after or before adding ingredients in method stages A and B.

Claims

1. A method for preparing a water based aerosol paint composition having a high concentration of coating material by selecting at least one pair of polymeric resin and propellant so that they will pass mutual compatibility test and after ensuring the mutual compatibility of polymeric resin and propellant preparing a water based aerosol paint composition from said polymeric resin and propellant said method comprising: selecting at least one pair of polymeric resin and propellant, wherein polymeric resin is selected among the groups A1-A9: A1) saponified/neutralized short oil alkyd which is in a water based solvent dilutable/emulsifiable and have less than 40% of fatty acids, A2) saponified/neutralized medium oil alkyd which is in a water based solvent dilutable/emulsifiable and have 40-60% of fatty acids, A3) short oil alkyd which is in a water based solvent emulsified/dispersed and have less than 40% of fatty acids, A4) medium oil alkyd which is in a water based solvent emulsified/dispersed and have 40-60% of fatty acids, A5) polyurethane modified alkyd being chained with mid oil, which in a water based solvent emulsified/dispersed and have 40-60% of fatty acids, A6) polyurethane modified alkyd chained with short oil having less than 40% of fatty acids and is in water based solvent emulsified/dispersed, A7) acrylic resin dispersible or emulsifiable in a water based solvent, A8) polyurethane modified acrylic resin dispersible or emulsifiable in a water based solvent, A9) polyurethane resin, and wherein the propellant is selected among the groups B1-B3 B1) dimethyl ether (DME), B2) propane, butane, isobutane, and mixtures thereof, B3); 2,2-dichloro-1,1,1-trifluoroethane; testing the mutual combability of the selected propellant-polymeric resin-pair in a pressurized vessel in the presence of water-based solvent, which mutual combability test comprises testing the mutual compatibility of propellant and polymeric resin for a group of concentration pairs of the propellant and the polymeric resin wherein each concentration pair comprises a member of polymeric resin having the first concentration, which member belong to group of polymeric resin concentrations and a member of propellant concentrations having the second concentration and which belong to group of propellant concentrations, wherein said polymeric resin group of concentrations consists of queue of polymeric concentrations which covers a test concentration range of polymeric resin, which test range is preferable from 25% w/w to 75% w/w and more preferable from 10% w/w to 90% w/w, and wherein said propellant group of concentrations consists of queue of propellant concentrations, which covers the test concentration range of propellant, which test range is preferable from 75% w/w to 25% w/w, more preferable from 90% w/w to 10% w/w; and wherein for said group of concentration pairs of propellant and polymeric resin within tested concentration range, the mutual compatibility is tested with test criteria C1-C3 which take into account at least following disturbances in paint material, formed paint film and spraying properties of the paint material out of the aerosol can: C1) disturbances in paint film formation: low gloss and transparency, abnormal formation of particles inside the film and C2) disturbances in spraying pattern (obstruction of a valve of an aerosol can) of paint material when sprayed out of the aerosol can and C3) disturbances in gloss or transparency of paint material when stored a time period inside the aerosol can; wherein for above mentioned test criteria C1-C3 failed compatibility (non-compatibility) of paint material comprising propellant, selected polymeric resin and water based-solvent which includes possible co-solvent, are following: C1: disturbances in film forming properties of paint material sprayed out from the aerosol can onto the target site, disturbance is measured as a gloss under 80, defined according to ISO 2813, and as a transparency over 5, when defined as an iodine colour number, according to standard DIN EN 1557 or DIN 6162, C2: disturbances in spraying properties of the aerosol paint composition detected as an aerosol can valve jamming due to paint material particles, C3: disturbances in gloss or transparency of aerosol paint composition when stored an extended time period in an aerosol can, disturbance is a gloss under 80 defined according to ISO 2813, and a transparency over 5, when defined as an iodine colour number, according to standard DIN EN 1557 or DIN 6162, and after passage of test criteria C1-C3 for ensuring the mutual compatibility of the selected propellant and the polymeric resin in the above defined mutual compatibility test within the tested concentration range of polymeric resin and the propellant group: providing into an aerosol can A) 50-85% w/w of coating material, consisting of nonvolatile content in the range of 17-60% w/w, preferable in the range of 30-50% w/w and volatile content in the range of 40-83% w/w preferable in the range of 50-70% w/w, wherein said volatile content comprises water or mixture of water with a water compatible co-solvent and which nonvolatile content comprises selected polymeric resin in the range of 35-90% w/w, color pigments, dispersing agents and possible fillers in the range of totally 0-30% w/w and additives up to 9% w/w provided that the said polymeric resin make up at least 8% w/w (dry weight at least 6% w/w) from the total weight of the water based aerosol paint composition, and B) selected propellant 15-50% w/w; sealing the can after or before adding ingredients in method stages A and B.

2. The method according to claim 1, wherein propellant is dimethyl ether (DME).

3. The method according to claim 1, wherein polymeric resin is selected among the groups A1-A6: A1) saponified/neutralized short oil alkyd which is in a water based solvent dilutable/emulsifiable and have less than 40% of fatty acids, A2) saponified/neutralized medium oil alkyd which is in a water based solvent dilutable/emulsifiable and have 40-60% of fatty acids, A3) short oil alkyd which is in a water based solvent emulsified/dispersed and have less than 40% of fatty acids, A4) medium oil alkyd which is in a water based solvent emulsified/dispersed and have 40-60% of fatty acids, A5) polyurethane modified alkyd being chained with mid oil, which in a water based solvent emulsified/dispersed and have 40-60% of fatty acids, A6) polyurethane modified alkyd chained with short oil having less than 40% of fatty acids and is in water based solvent emulsified/dispersed.

4. The method defined in claim 1, wherein water-based solvent is either a) water without co-solvent or b) a mixture of water and water-compatible co-solvent wherein the amount of co-solvent is in the range of 0.1-4% w/w preferable in the range of 0.1-2% w/w from the total weight of the aerosol paint composition.

5. The method defined in claim 4, wherein a mixture of water and water-compatible co-solvent said co-solvent is one or more solvents selected from the group consisting of lower alcohols, glycol ethers, alkyl ethers of ethylene glycol or propylene glycol, wherein the total concentration of said co-solvents is in the range of 0.1-4% w/w calculated from the total weight of the aerosol paint composition.

6. The method defined in claim 1, wherein the water-based aerosol paint resin to be prepared have passed the mutual compatibility test of the propellant and the polymeric resin, within the tested concentration range of polymeric resin and propellant group and have a shelf life of several months.

7. The method defined in claim 1, for preparing a water based aerosol paint composition, wherein either styrene, styrene-butadiene or latex resins are excluded.

8. The method defined in claim 1, for preparing a water based aerosol paint composition, wherein Tg (glass transition state) of the polymeric resin is over 55 and/or MTF (minimum film formation temperature) of the polymeric resin is under 20° C.

9. The method defined in claim 1, which method comprises in stages A and B: filling an aerosol can with the coating material, closing the can and filling the closed can with propellant, which is dimethyl ether (DME) before or after sealing the aerosol can.

10. The method defined in claim 1, wherein the filling volume of the can is either 400 ml or 675 ml.

11-27. (canceled)

Description

EXAMPLES FROM COMPOSITIONS

[0184] Paint Compositions for Aerosol Cans

[0185] Following compositions were prepared into an aerosol can by filling an aerosol can with the coating material then closing the can. The closed can was filled with liquefied propellant dimethyl ether (DME). The filling volume of the can was either 400 ml or 675 ml. In any of the given examples can be used all binders given in table 1.

[0186] Polymeric resins used in examples contain water and their dry matter content was usually 6-30%. In brackets is given the proportion of dry resin.

Example 1

High Gloss Top Coat

[0187]

TABLE-US-00009 Ingredients % w/w Necowell 4300 60.00 (25.8) Dispersing aid 0.40 Drier 0.06 Defoamer 0.30 color pastes 10.00 Thickener 0.25 Aerosil 200 (SiO2 fumed) 0.50 Water 6.49 Dimethyl ether 22.00 Total 100.00 (34)

[0188] Instead of Necowell 4300 also other binders mentioned in table 1 can be used.

Example 2

Anti Rust Primer

[0189]

TABLE-US-00010 Ingredient % w/w Synaqua 4804 53.40 (26.7) Dispersing aid 0.60 Defoamer 0.30 Iron Oxyde RED paste 8.00 Calcium modified silica gel 5.00 Bentonite 0.60 thickener 0.16 Water 3.50 dimethyl ether 27.00 Total 100.00 (39)

[0190] Instead of Synaqua 4804 also other binders mentioned in table 1 can be used.

Example 3

Clear Top Coat

[0191]

TABLE-US-00011 Ingredient % w/w Worleesol E330W 57.00 (24) Defoamer 0.30 Thickener 0.35 Flow/slip additive 0.10 Flow/slip additive 20.25 Dimethyl ether 22.00 Total 100.00 (24)

[0192] Instead of binder Worleesol E330W can also be used WorleeSol NW 410. Also other binders mentioned in table 1 can be used.

Example 4

[0193] Fast Drying Color High Gloss Top Coat with Excellent Anti Corrosion Proportions

TABLE-US-00012 Ingredient % w/w Worleesol E927W 25.00 (10) Domalkyd 0545 40 Wa or Necowel 586 N 30.00 (12) dispersing agent 0.25 defoamer 0.20 flow/slip additive 0.18 thickner (newtonian) 0.10 thickner (tixothrope) 0.16 mix of collar paste's 10.00 Water 11.11 Dimethyl ether 23.00 Total 100.00 (30)

[0194] Instead of Worleesol E927W and Domalkyd 0545 40 Wa or Necowel 586 N also other binders mentioned in table 1 can be used.

Example 5

[0195] A typical water-based aerosol base paint of the invention comprises polyurethane-modified resin 80-100 g (binder), water 100-150 g, various additives 2-11 g and dimethyl ether (DME) 75-95 g, packed for example in an aerosol bottle having a filling volume of 400 ml.

[0196] One typical ready-to-use aerosol base paint of the invention, present in a pressurized aerosol bottle with a filling volume of 400 ml, was prepared as follows: [0197] the polyurethane-modified resin and additives were dispensed into an aerosol bottle, [0198] the propellant (DME) was added into the aerosol bottle and the bottle was sealed to become airtight.

[0199] Thus, the pressurized aerosol bottle having a filling volume of 400 ml contained the following aerosol base paint components in liquid phase:

TABLE-US-00013 Ingredient amount/g amount/w-% Polyurethane-modified alkyd resin 92.7 30.1 (12.6) Flow promoter (Capston) 0.8 0.2 Pigment stabilizer (Dextrol) 0.9 0.3 Thickener (Rheolate) 1.8 0.6 Drying agent (Additol) 3.3 1.1 Drying accelerator 2.3 0.7 Monoethanolamine (corrosion inhibitor) 0.8 0.2 Water 121.5 39.5 DME (dimethyl ether) 83.6 27.2 Total 307.0 100.0 (14)

[0200] The density of this aerosol base paint was about 1 g/cm.sup.3, whereby the volume occupied by the liquid phase of the aerosol bottle's filling volume (400 ml) was about 300 ml.

[0201] Such an aerosol base paint is combustible as such, but have a high binder content (about 30% by weight) and relatively low amount of dimethyl ether, DME (27% by weight) and can be used for preparing also non-flammable aerosol paint compositions.

[0202] This aerosol base paint is compatible with most of the commercial toning equipment for water-based paints, i.e. it can have a pigment (coloring paste) dispensed therein in a mechanized manner with dispensing devices having a dosing accuracy of 0.1-0.2 ml.

[0203] This aerosol base paint makes it possible to provide a paint coating with any desired gloss level (matte, semi-gloss, glossy)

[0204] One and the same aerosol base paint lends itself to being toned for a precisely desired tint for example with the RAL color matching system (168 color tones) or with the NCS color tone system (1668 color tones).

[0205] Instead of polyurethane-modified alkyd, it is also possible to use alkyd, epoxy-modified alkyd, and some styrene-butadiene emulsions/dispersions (latexes) having low transition glass temperature.

Example 6

[0206] A base paint for preparing a non-flammable paint into an aerosol can;

[0207] First aerosol base paint modified in terms of the amount of alkyd resin

TABLE-US-00014 Ingredient amount/g amount/w-% Polyurethane-modified alkyd resin 67.7 22.0 (10) Flow promoter (Capston) 0.8 0.2 Color pigment stabilizer (Dextrol) 0.9 0.3 Thickener (Rheolate) 1.8 0.6 Drying agent (Additol) 3.3 1.1 Drying accelerator 2.3 0.7 Monoethanolamine (corrosion inhibitor) 0.8 0.2 Water 146.5 47.6 DME 83.6 27.2 Total 307.0 100.0 (11.73)

[0208] In the aerosol base paint of example 1, having been packed into an aerosol bottle with a filling volume of 400 ml, the amount of alkyd resin was modified according to which components were added from a filling cup of 100 ml into the aerosol base paint present in the aerosol bottle. The filling cup was again functionally in communication with a toning and dispensing device whose minimum dosing amount was 0.1 ml of coloring paste.

[0209] The first aerosol base paint, which was modified in terms of the amount of alkyd resin, had been modified in such a way that it could be supplemented from the filling cup of a toning and dispensing device with a coloring paste in the amount of 1-35 ml corresponding to each color tone recipe, as well as with a binder and water 50 ml in total (50% by volume of water, 50% by volume of polyurethane-modified alkyd resin). Thereby is obtained an aerosol paint toned to readiness, the space occupied thereby being 350-400 ml of the aerosol bottle with a filling volume of 400 ml.

Example 7

Second Aerosol Base Paint Modified in Terms of the Amount of Alkyd Resin:

[0210]

TABLE-US-00015 Component amount/g amount % w/w Polyurethane-modified  42.7 13.9 alkyd resin   (6.95) Flow promoter (Capston)   0.8  0.2 Color pigment stabilizer (Dextrol)   0.9  0.3 Thickener (Rheolate)   1.8  0.6 Drying agent (Additol)   3.3  1.1 Drying accelerator   2.3  0.7 Monoethanolamine   0.8  0.2 (corrosion inhibitor) Water 171.5 55.8   (8.78) DME  83.6 27.2 Total 307.0 100.0 

[0211] In the second modified aerosol base paint, the amount of alkyd resin in the aerosol base paint of example 1 had been changed in such a way that it could be supplemented from a filling cup of the toning and dispensing device with a coloring paste in the amount of 1-35 ml corresponding to each color tone recipe, and with 50 ml of water. Thereby is obtained an aerosol paint toned to readiness, the space occupied thereby being 350-400 ml of the aerosol bottle with a filling volume of 400 ml.

Examples 8A and 8B

Example 8A

[0212] The aerosol base paint of example 5 was modified to get a white base paint and it was packed into an aerosol can with a filling volume of 400 ml and then toned in a mechanized manner with a commercial dispensing machine (see FIG. 1) whose minimum dispensing amount was 0.1 ml of color paste compound.

[0213] The color paste mixture was dispensed into a filling cup of the dispensing machine in an amount 1-50 ml corresponding to color tone recipe, and then into the same filling cup was added 40 ml of binder (polyurethane-modified alkyd resin). Thereby was obtained an aerosol paint toned to readiness for use, the space occupied thereby being 350-400 ml of the aerosol can with a filling volume of 400 ml.

Part A: Filled Aerosol can

[0214]

TABLE-US-00016 White base paint 247 g (185 ml) DME (dimethyl ether)  73 g (110 ml)

Part B: Filling Cup, Added to Aerosol can of Part A

[0215]

TABLE-US-00017 Domalkyd 0545 40 Wa or .sub.   40 g Necowel 586 N (binder) (40% w/w emulsion in water) Color paste mixture 20-50 g (20-50 ml)

Parts A+B Combined, Main Components of the Formed Aerosol Paint

[0216]

TABLE-US-00018 Binder (Domalkyd 0545 40 Wa .sub.   31% w/w or Necowel 586 N) Water .sub.   10% w/w DME .sub.   19% w/w TiO.sub.2 .sub.   25% w/w Other pigments 5-12% w/w Additives 5-12% w/w, wherein each of the additive is 0.1-1.5% w/w added

White Base Paint Composition and its Volatile Organic Compounds

Polyurethane Modified Alkyd Emulsion

[0217]

TABLE-US-00019 Domalkyd 0545 40 Wa or Necowel 586 N 40% w/w in water, VOC Free Siccatief 0.22% w/w Drier Dextrol OC-180 dispersing agent) TiO.sub.2 Capstone SF 65 surface tension modifier, VOC free BYk 349 surface tension modifier Rheolate 310 rheology modifier, VOC free Diosperbyk 199 Wetting and dispersive agent, Voc free, pigment stabilizer AMP pH modifier Water (demineralized) Acemat Ok 520 solid matting agent

[0218] As can be seen above none of the additives, binder or pigments contains any volatile organic compounds (VOC). The only VOC-source was DME having weight of 19% w/w of the total weight of the readymade aerosol paint in the can (400 ml). The VOC-content of this aerosol paint is 19% and it was non-flammable in a subsequent test.

Example 8B

[0219] The aerosol base paint of example 1 was modified to get a clear base paint and it was packed into an aerosol can with a filling volume of 400 ml and then toned in a mechanized manner with a commercial dispensing machine (see FIG. 1) whose minimum dispensing amount was 0.1 ml of color paste compound.

[0220] The color paste mixture was dispensed into a filling cup of the dispensing machine in an amount 1-50 ml corresponding to color tone recipe, and then into the same filling cup was added 40 ml of binder (polyurethane-modified alkyd resin). Thereby was obtained an aerosol paint toned to readiness for use, the space occupied thereby being 350-400 ml of the aerosol can with a filling volume of 400 ml.

Part A: Filled Aerosol can

[0221]

TABLE-US-00020 Binder mix clear 185 g (185 ml) DME (dimethyl ether)  73 g (110 ml)

Part B: Filling Cup, Added to Aerosol can of Part A

[0222]

TABLE-US-00021 Domalkyd 0545 40 Wa or Necowel 586 N (binder) .sub.   40 g (40% w/w emulsion in water) Color paste mixture 20-50 g (20-50 ml)

Parts A+B Combined, Main Components of the Formed Aerosol Paint

[0223]

TABLE-US-00022 Binder (Domalkyd 0545 40 Wa 48% w/w or Necowel 586 N) Water  6% w/w DME 21% w/w Pigments 7-15% w/w Additives 5-10% w/w, wherein each of the additive is 0.1-1.5% w/w added

Clear Binder Mix Base Paint Composition and its Volatile Organic Compounds

Polyurethane Modified Alkyd Emulsion

[0224]

TABLE-US-00023 Domalkyd 0545 40 Wa or Necowel 586 N 40% w/w in water, VOC Free Borchi oxy coat, Voc free Drier Dextrol OC-180 dispersing agent) TiO.sub.2 Capstone SF 65 surface tension modifier, VOC free BYk 349 surface tension modifier Rheolate 310 rheology modifier, VOC free Diosperbyk 199 Wetting and dispersive agent, Voc free, pigment stabilizer AMP pH modifier Water (demineralized)

[0225] As can be seen from above, none of the additives, binders or pigments contain any volatile organic compounds (VOC). The only VOC-source was DME having weight of 19% w/w of the total weight of the readymade aerosol paint composition in the can (400 ml). The VOC-content of this aerosol paint is 21% w/w and the paint was non-flammable in a subsequent test.

[0226] In examples 9-11 have been presented some exemplary, non-restricting examples of aerosol paint which may be flammable in a relevant test. Again, in the brackets have been presented dry weight percents for some main components of the aerosol paint composition.

Example 9

[0227]

TABLE-US-00024 Ingredients % w/w Necowell 4300  42.00 (18.06) Dispersing aid 0.28 Drier 0.04 Defoamer 0.21 color pastes 7.00 (4.9) Thickener 0.18 Aerosil 200 (SiO2 fumed) 0.35 Water 4.94 Dimethyl ether 45.00  Total 100.00 (23.80)

Example 10

[0228]

TABLE-US-00025 Ingredient % w/w Worleesol E330W 38.00 (15.96) Defoamer 0.20 (0.02) Thickener  0.23 Flow/slip additive  0.08 Water 13.49 Dimethyl ether 48.00 Total 100.00 (16.29) 

Example 11

[0229]

TABLE-US-00026 Ingredient amount/w-% Polyurethane-modified alkyd resin 23.15 (11.58) Flow promoter (Capston)  0.15 Pigment stabilizer (Dextrol)  0.23 Thickener (Rheolate)  0.46 Drying agent (Additol) 0.85 (0.05) Drying accelerator  0.54 Monoethanolamine (corrosion inhibitor)  0.15 Color pigment 7.00 (5.00) Water 24.28 DME (dimethyl ether) 44.00 Total 100.0 (18.16)

Example 12

Comparison and Combability Tests

12a) Comparison Test for Ageing of an Aerosol Paint Composition

General

[0230] The spray pattern delivered from an aerosol can is a combination of the content of the can proportions, being the amount of liquefied propellant, the pressure, viscosity and of course how fine are the solid particles that have to be transported through the valve and the actuator.

[0231] As an indication the diameter of the openings in the valve and actuator during the spraying are between 0.1 mm to 0.5 mm.

[0232] This means if paint in the can starts to flocculate or is the binder gets attacked by the propellant (DME) and cloaks together this will have a direct impact on the spray result. This can lead to solid particles disturbing the wet film and being visible in the dry film until totally blocking of the valve and actuator.

[0233] Aging tests have been done with the formulations 1-3.

Formulation 1

[0234] Colored top coat based on mix of polyurethane modified short and medium oil alkyd emulsion

TABLE-US-00027 Ingredient amount/w-% Resin 1 Worleesol E927W 25.00 10)  Resin 2 Domalkyd 0545 40 Wa or Necowel 586 N 30.00 (12) dispersing agent Byk 191  0.25 defoamer Byk 015  0.20 flow/slip additive tego glide 110  0.18 thickener (Tixothrope) Tafigel pur 60  0.10 thickener (Tixothrope) Byk 525  0.16 color paste mixture 10.00 (7)  water 11.11 Dimethyl ether 12.00 Total   100.00 (29.89)

Formulation 3I: Acrylic Dispersion Based Colored Top Coat

[0235]

TABLE-US-00028 Ingredient % w/w EPS 294 (405 w/w in water) 35.00 (14)    thickener Rheolate 310  0.40 Tego glide 110  0.30 Bentone SD2  0.13 Color pastes 8.00 (5.6)  Texanol (solvent no VOC) 3-pentanediol,2,2,4-trimethyl-monoisobutyrate)  4.00 water 17.17 Dimethyl ether (DME) 35.00 Total 100.00 (24.43) 

Formulation 3I

Clear Acrylic Varnish:

[0236]

TABLE-US-00029 Ingredient % w/w Joncryl 538 (acrylic dispersion) 32.40 (15.07) Joncryl 683 (low mol weight acryl 98% in solvent)  9.00 (8.82)  diethyleneglycol monobutylether (non-flammable  4.00 but it will burn. UEL 6.2 LEL 0.9% in air) Isopropanol  3.00 Defoamer byk 015  0.30 Acemat 520 (hydrophobic fumed silica)  0.40 Thickener DSX 3290  0.55 water 10.35 Dimethyl ether 40.00 Total 100.00 (24.99) 

Results

[0237] After aging tests in the oven at 40° C. and 20° C. with intervals of 1 week spray tests have been performed.

12b) Compatibility Test Method Between Propellant and Binder

[0238] Test method to determine compatibility between water-based binders and liquified propellants.

[0239] Compatibility tests have been also done with the formulations 1-3 (see below).

[0240] Description and purpose of the test.

[0241] Testing compatibility of water-based binders with hydrocarbon propellant, specifically dimethyl ether (DME) in various mix ratio's together with the amount cosolvent if needed for the film forming of the binder. Binder and propellant were both as homogenous solutions and these solutions were then mixed together. In tests it is given the weights binder dispersion/emulsion and liquid propellant (wet/wet).

[0242] Binder dispersions and emulsions can be disturbed by adding hydrocarbon or more generally organic liquids like dimethyl ether DME (DME is at least partly liquid in an aerosol can).

[0243] Cause can be disturbance of the binder emulsion or dispersion that can lead to and agglomerate of binder with a particle size too big the be handled by the aerosol valve and will lead to a blocked and non-functional product.

[0244] By disturbing the emulsion and/or dispersion the protection of the binder particles will be less and the can be attacked by the liquid DME that can result in tackifying of the particles which will lead to agglomerates with the above-mentioned blocking effect of the aerosol valve. These agglomerates of binder will also disturb film forming process. In a case size of the binder particles (agglomerates) are 35-40 um they can be visually inspected.

[0245] To test the compatibility of the binders and the DME, aerosol fillings comprising paint material composition made of DME, binders, possible co-solvents and water is made in various concentrations, preferably in glass aerosol cans to observe the behaviour of the mixtures under pressure. If no glass aerosol cans are available normal metal aerosol cans can be used also.

Test Criteria:

[0246] Functionality of the spray can or bottle meaning smooth spray pattern; no blocking of actuator valve etc.

[0247] In case of use glass aerosols; observe irregularities in the mixture in the package.

[0248] Spraying of the paint coating material onto target surface/site and detecting film forming properties: [0249] Film forming: a smooth paint film should be formed without any visible binder parts that do not contribute to film forming process. Any binder particle should be below 35-40 μm. [0250] Transparency or discoloration of the formed paint film and gloss of the paint film should be right.

[0251] Paint film gloss should be over 80 when determined according to ISO 2813 or transparency, (clarity, haziness) of the film should be under 4-5 when determined as iodine colour number. This can be done according to standard DIN EN 1557 and DIN 6162. If transparency of paint film or paint material composition inside the aerosol can is inspected visually saybolt-colour scale (ASTM D 156) can be used.

[0252] Iodine value can be determined by various methods (see for example Wikipedia: methods for determination of iodine value).

[0253] Instead of Iodine colour number also Gardner color scale can be used (ASTM standard D1544 and D6045). [0254] Drying time of the film is appropriate. This test criteria is somewhat subjective and should be applied with care because a proper paint film quality is most important aspect.

Combability Tests: Results

[0255]

TABLE-US-00030 Test 1 Binder: Joncryl 538 together with co-solvent inside criteria Binder co-solv. Dme 0 1 2 3 4 5 6 7 8 9 10 11 12 13 25 0.75 74.25 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 30 0.9 69.1 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 35 1.05 63.95 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 40 1.2 58.8 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 45 1.35 53.65 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 50 1.5 48.5 + + + + + + + + + + + +/− +/− +/− 55 1.65 43.35 + + + + + + + + + + + +/− +/− +/− 60 1.8 38.35 + + + + + + + + + + + +/− +/− +/− 65 1.95 33.05 + + + + + + + + + + + + + +/− 70 2.1 27.9 + + + + + + + + + + + + + +/− 75 2.25 22.75 + + + + + + + + + + + + + +/− inside + ok +/− particle size is growing − particles form sediment on the bottem Binder: Joncryl 538 together with co-solvent spray pattern criteria Binder co-solv. Dme 0 1 2 3 4 5 6 7 8 9 10 11 12 13 25 0.75 74.25 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 30 0.9 69.1 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 35 1.05 63.95 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 40 1.2 58.8 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 45 1.35 53.65 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 50 1.5 48.5 + + + + + + + + + + + +/− +/− +/− 55 1.65 43.35 + + + + + + + + + + + +/− +/− +/− 60 1.8 38.35 + + + + + + + + + + + +/− +/− +/− 65 1.95 33.05 + + + + + + + + + + + + + +/− 70 2.1 27.9 + + + + + + + + + + + + + +/− 75 2.25 22.75 + + + + + + + + + + + + + +/− spray + spray ok +/− spray pattern interrupted by to big solid particles − actuator/valve blocked gloss criteria Binder co-solv. Dme 0 1 2 3 4 5 6 7 8 9 10 11 12 13 25 0.75 74.25 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 30 0.9 69.1 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 35 1.05 63.95 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 40 1.2 58.8 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 45 1.35 53.65 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 50 1.5 48.5 + + + + + + + +/− +/− +/− +/− +/− +/− +/− 55 1.65 43.35 + + + + + + + + + +/− +/− +/− +/− +/− 60 1.8 38.35 + + + + + + + + + + +/− +/− +/− +/− 65 1.95 33.05 + + + + + + + + + + + + +/− +/− 70 2.1 27.9 + + + + + + + + + + + + + +/− 75 2.25 22.75 + + + + + + + + + + + + + +/− gloss └60° +++ 80-100 ++ 60-80 + 40-60 − <40

TABLE-US-00031 Test 2 Binder: Synthalat PWM 883   together with co-solvent inside criteria Binder co-solv. Dme 0 1 2 3 4 5 6 7 8 9 10 11 12 13 25 0.75 74.25 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 30 0.9 69.1 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 35 1.05 63.95 + + + + +/− +/− +/− +/− +/− +/− − − − − 40 1.2 58.8 + + + + +/− +/− +/− +/− +/− +/− − − − − 45 1.35 53.65 + + + + +/− +/− +/− +/− +/− +/− − − − − 50 1.5 48.5 + + + + + + + + + + + +/− +/− +/− 55 1.65 43.35 + + + + + + + + + + + +/− +/− +/− 60 1.8 38.35 + + + + + + + + + + + +/− +/− +/− 65 1.95 33.05 + + + + + + + + + + + + + +/− 70 2.1 27.9 + + + + + + + + + + + + + +/− 75 2.25 22.75 + + + + + + + + + + + + + +/− inside + ok +/− particle size is growing − particles form sediment on the bottem Binder: Joncryl 538 together with co-solvent spray pattern criteria Binder co-solv. Dme 0 1 2 3 4 5 6 7 8 9 10 11 12 13 25 0.75 74.25 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 30 0.9 69.1 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 35 1.05 63.95 + + + +/− +/− +/− +/− +/− +/− +/− − − − − 40 1.2 58.8 + + + + +/− +/− +/− +/− +/− +/− − − − − 45 1.35 53.65 + + + + + + +/− +/− +/− +/− − − − − 50 1.5 48.5 + + + + + + + + + + + +/− +/− +/− 55 1.65 43.35 + + + + + + + + + + + +/− +/− +/− 60 1.8 38.35 + + + + + + + + + + + +/− +/− +/− 65 1.95 33.05 + + + + + + + + + + + + + +/− 70 2.1 27.9 + + + + + + + + + + + + + +/− 75 2.25 22.75 + + + + + + + + + + + + + +/− spray + spray ok +/− spray pattern interrupted by to big solid particles − actuator/valve blocked gloss criteria Binder co-solv. Dme 0 1 2 3 4 5 6 7 8 9 10 11 12 13 25 0.75 74.25 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 30 0.9 69.1 + + +/− +/− +/− +/− +/− +/− +/− +/− − − − − 35 1.05 63.95 + + + +/− +/− +/− +/− +/− +/− +/− − − − − 40 1.2 58.8 + + + +/− +/− +/− +/− +/− +/− +/− − − − − 45 1.35 53.65 + + + + + +/− +/− +/− +/− +/− − − − − 50 1.5 48.5 + + + + + + + +/− +/− +/− +/− +/− +/− +/− 55 1.65 43.35 + + + + + + + + + +/− +/− +/− +/− +/− 60 1.8 38.35 + + + + + + + + + + +/− +/− +/− +/− 65 1.95 33.05 + + + + + + + + + + + + +/− +/− 70 2.1 27.9 + + + + + + + + + + + + + +/− 75 2.25 22.75 + + + + + + + + + + + + + +/− gloss └60° +++ 80-100 ++ 60-80 + 40-60 − <40 indicates data missing or illegible when filed

TABLE-US-00032 Test 3 Binder: Joncryl 1537 together with co-solvent inside criteria Binder co-solv. Dme 0 1 2 3 4 5 6 7 8 9 10 11 12 13 25 0.75 74.25 − test stoped 30 0.9 69.1 − test stoped 35 1.05 63.95 − test stoped 40 1.2 58.8 − test stoped 45 1.35 53.65 − test stoped 50 1.5 48.5 − test stoped 55 1.65 43.35 − test stoped 60 1.8 38.35 − test stoped 65 1.95 33.05 − test stoped 70 2.1 27.9 + + +/− +/− +/− +/− +/− test stoped 75 2.25 22.75 + + +/− +/− +/− +/− +/− + test stoped inside + ok +/− particle size is growing − particles form sediment on the bottem Binder: Joncryl 538 together with co-solvent spray pattern criteria Binder co-solv. Dme 0 1 2 3 4 5 6 7 8 9 10 11 12 13 25 0.75 74.25 − test stoped 30 0.9 69.1 − test stoped 35 1.05 63.95 − test stoped 40 1.2 58.8 − test stoped 45 1.35 53.65 − test stoped 50 1.5 48.5 − test stoped 55 1.65 43.35 − test stoped 60 1.8 38.35 − test stoped 65 1.95 33.05 − test stoped 70 2.1 27.9 + + +/− +/− +/− +/− +/− test stoped 75 2.25 22.75 + + +/− +/− +/− +/− +/− + test stoped spray + spray ok +/− spray pattern interrupted by to big solid particles − actuator/valve blocked gloss criteria Binder co-solv. Dme 0 1 2 3 4 5 6 7 8 9 10 11 12 13 25 0.75 74.25 −−− test stoped 30 0.9 69.1 −−− test stoped 35 1.05 63.95 −−− test stoped 40 1.2 58.8 −−− test stoped 45 1.35 53.65 −−− test stoped 50 1.5 48.5 −−− test stoped 55 1.65 43.35 −−− test stoped 60 1.8 38.35 −−− test stoped 65 1.95 33.05 −−− test stoped 70 2.1 27.9 +/− +/− − test stoped 75 2.25 22.75 +/− +/− − test stoped gloss └60° +++ 80-100 ++ 60-80 + 40-60 − <40

CONCLUSIONS

Formulation I

[0256] 1 week high gloss good opacity no spray defects. Eventually this formulation has a shelf life of app 3 years at 20° C.

Formulation 2

[0257] 1 week a little lower gloss than fresh can at start of the test. opacity ok 2 weeks solid particles in the spray interrupting the spray pattern and visible in the wet and dry film.

[0258] 3 weeks after vigorously shaking the shaking balls were free a pray attempt was made but the valve/actuator system was blocked completely. After degassing the can (uncultured with a pin) the paint in the can was observed. It showed total coagulated binder and color pigment.

[0259] Conclusion: not stable, short shelf life.

Formulation 3

[0260] Immediately (timeframe appr. 1h) after making the can it was impossible to spray for the moment the actuator was pushed down the valve and the actuator blocked completely.

[0261] After degassing the can (uncultured with a pin) the paint in the can was observed. It showed total coagulated binder and color pigment.

[0262] Conclusion: Nor stable, very short shelf life

[0263] Conclusions: Acrylic dispersions (formula 1 and 2) of water-borne aerosol paint do not have enough shelf life, because these acrylic resins are incompatible with propellant dimethyl ether (DME). When alkyd polyurethane modified short and medium oil alkyd emulsion were used as resin enough shelf life was achieved.