POLYVINYL BUTYRAL DISPERSIONS

Abstract

A stable aqueous film forming dispersion comprising:

a polymer selected from the group consisting of: polyvinyl butyral, polyvinyl acetyl, ethylene vinyl acetate, vinyl acetate and mixtures thereof:

a plasticiser;

an emulsifier; and

a water soluble organometallic crosslinking agent.

Claims

1. A stable aqueous film forming dispersion comprising: a polymer selected from the group consisting of: polyvinyl butyral, polyvinyl acetal, ethylene vinyl acetate, polyvinyl acetate and mixtures thereof: a plasticiser; an emulsifier; and a water soluble organic metallic crosslinking agent.

2. A dispersion as claimed in claim 1, wherein the polymer is polyvinyl butyral.

3. A dispersion as claimed in claim 1, wherein the polymer has a molar mass in the range of 10,000 to 120,000.

4. A dispersion as claimed claim 1, comprising an oil-in water dispersion.

5. A dispersion as claimed in claim 1, wherein the polymer comprises completely, or in part, recycled or reclaimed polyvinyl butyral.

6. A dispersion as claimed in claim 1, wherein the amount of the polymer is in the range of 10 wt % to 50 wt %.

7. A dispersion as claimed in claim 1 which the polymer is polyvinyl butyral, wherein the amount of polymer is 15 wt % to 45 wt %.

8. A dispersion as claimed in claim 1, wherein the plasticiser is selected from the group consisting of castor oil, butyl ricinoleate, sebacates, benzoates, adipates and phthalates.

9. A dispersion as claimed in claim 8, wherein the amount of the plasticiser is 2 wt % to 20 wt %.

10. A dispersion as claimed in claim 1, wherein the crosslinking agent is an organic titanium or zirconium salt.

11. A dispersion as claimed in claim 1, wherein the crosslinking agent is selected from the group consisting of ammonium zirconium carbonate, titanium ammonium lactate, triethanolamine titanate and mixtures thereof.

12. A dispersion as claimed in claim 1, wherein the amount of the crosslinking agent is 0.05 wt % to 1.0 wt %.

13. A dispersion as claimed in claim 1, wherein the emulsifier is selected from fatty acid soaps of saturated or unsaturated C3 to C22 carboxylic acids in an amount of 1.5 wt % to 10 wt %.

14. A method of preparation of an aqueous film forming emulsion comprising the steps of: heating a mixture comprising a polymer selected from the group consisting of: polyvinyl butyral, polyvinyl acetal, ethylene vinyl acetate, vinyl acetate and mixtures thereof: a plasticiser; an emulsifier; and water, with stirring under pressure at a temperature from 110° C. to 150° C., to form a water-in oil emulsion plasticised polymer melt; adding water to the melt to cause phase inversion to form an oil-in water emulsion; cooling the oil-in water emulsion to a temperature between 0° C. and 40° C.; adding a water soluble organic metallic crosslinking agent and optional further additives to form a stable aqueous film forming dispersion.

15. A method as claimed in claim 14, for preparation of a stable aqueous film forming dispersion as claimed in claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] FIGS. 1 through 9 are referenced in the Examples, below:

[0008] FIG. 1 shows the Water Uptake % versus Immersion Time for various PVB films after 72 hours, drying at ambient temperature.

[0009] FIG. 2 shows the Water Uptake % versus Immersion Time for various PVB films after 24 hours, drying at ambient temperature.

[0010] FIG. 3 shows the Water Uptake % versus Immersion Time for various PVB films after 24 hours, drying at ambient temperature and 1 hour at 60° C.

[0011] FIG. 4 shows the Water Uptake % versus Immersion Time for various PVB films, dried for 72 hours at ambient temperature.

[0012] FIG. 5 shows the Water Uptake % versus Immersion Time for various PVB films, dried for 72 hours at ambient temperature (Competitor A).

[0013] FIG. 6 shows the Water Uptake % versus Immersion Time for various PVB films, dried for 24 hours at ambient temperature.

[0014] FIG. 7 shows the Water Uptake % versus Immersion Time for various PVB films, dried for 24 hours at ambient temperature (Example 3a). FIG. 8 shows the Water Uptake % versus Immersion Time for various PVB films, dried for 24 hours at ambient temperature, plus 1 hour at 60° C.

[0015] FIG. 9 shows Water Uptake % versus Immersion Time for various PVB films, dried for 24 hours at ambient temperature, plus 1 hour at 60° C. (Example 3a).

DETAILED DESCRIPTION

[0016] PVB resins possess three functionalities. These are acetyl, residual hydroxyl from the base PVOH used during manufacture, and residual acetate functionalities from base vinyl acetate polymer used to make vinyl alcohol. PVB with various ratios of acetyl, hydroxyl and acetate are available from a number of companies, e.g. Kuraray, Eastman, CCP, Sekisui. PVB is available in a number of molecular weights and functionalities.

[0017] According to a first aspect of the present invention, a stable aqueous film forming dispersion comprises:

[0018] a polymer selected from the group consisting of: polyvinyl butyral, polyvinyl acetyl, ethylene vinyl acetate, polyvinyl acetate and mixtures thereof:

[0019] a plasticiser;

[0020] an emulsifier; and

[0021] a water soluble organic metallic crosslinking agent.

[0022] The crosslinking agent may be an organic metal salt.

[0023] A preferred polymer is polyvinyl butyral. Especially advantageous polyvinyl butyral polymers have one or more properties selected from the following properties.

[0024] The molar mass may be in the range 10,000-120,000. Exemplary polymers have a molar mass in the ranges 15,000-30,000, 50,000-60,000 and 95,000-110,000.

[0025] The hydroxyl content may be in the range of 12% to 27%, alternatively 18% to 21%.

[0026] The glass transition temperature (Tg) may be in the range 66° C. to 84° C., alternatively 64° C. to 73° C.

[0027] The residual acetate content may be in the range 0% to 18%, alternatively 1% to 4%.

[0028] The dispersion may be provided as an oil-in-water dispersion, which is liquid at ambient temperatures.

[0029] The following polymers have been found to be particularly advantageous.

[0030] Mowital/Pioloform B20H (ex. Kuraray GmbH). This is a low molecular weight PVB with typical molar mass of between 15000-30000 g/mol, Tg of 64° C., hydroxyl content of between 18-21% wt., and residual acetate of 1-4% wt. It is supplied in powder form with a total solids of ≧97.5% and a 10% ethanol solution viscosity between 14-20 mPa.Math.s.

[0031] Mowital B30H (ex. Kuraray GmbH). This is a medium molecular weight PVB with a typical molar mass of 25,000-38,000 g/mol, Tg of 68° C., hydroxyl content of 18-21% wt %, residual acetate content of 1-4% and a 10% ethanol solution viscosity of 35-60 mPa.Math.s.

[0032] Poly G (=Mowital B75H. Ex. Kuraray GmbH). This is a high molecular weight PVB with molar mass between 95,000-110,000, Tg of 73° C., hydroxyl content 18 wt % to 21 wt % and residual acetate content 1 wt % to 4 wt %. It is supplied as powder (B75H), flake or in granular (Poly G) form with TS of ≧97.5%. and a 5% ethanol solution viscosity of between 60-100mPa.Math.s.

[0033] Mowital/Pioloform B6OH (ex. Kuraray GmbH). This is a high MW PVB with typical molar mass 50,000-60,000, Tg of 70° C., Hydroxyl content 18-21% wt and residual acetate of 1-4% wt. It is supplied in powder form with TS≧97.5% and a 10% ethanol solution viscosity of 160-260 mPa.Math.s.

[0034] PVB resins with higher or lower levels of residual hydroxyl content of such Mowital HH (—OH residual: 11-16% wt) and Mowital T (—OH residual 24-27% wt) can also be used as can any PVB resins with molar masses between 10,000-120,000. Furthermore, PVB resins with lower degree of acetylation and higher residual acetate of up to 18% can be selected for emulsification such as Mowital BX 860 (ex. Kuraray GmbH).

[0035] Alternatively, the polymer may comprise completely or in part recycled or reclaimed PVB such as may be recovered from laminated automobile and architectural glass.

[0036] The amount of the polymer may be 10 wt % to 50 wt %, alternatively 35 wt % to 45 wt %.

[0037] In embodiments in which the polymer is polyvinyl butyral, the amount may be 15 wt % to 45 wt %, alternatively 30 wt % to 45 wt %.

[0038] In embodiments the polyvinyl butyral is plasticised to enable film formation at ambient temperature using a suitable plasticiser known by those practised in the art. The plasticiser may be selected but not exclusively from: castor oil, butyl ricinoleate, dibutyl sebacate, glycerol trisebacate, adipates and phthalates including triethylene glycol bis-(2-ethyl hexanoate) and mixtures thereof. The amount of plasticiser may be 2 wt % to 20 wt % of the emulsion alternatively 10 wt % to 18 wt %.

[0039] The crosslinking agent may comprise a water dispersible latent organic metallic crosslinking agent, such as an organic metal salt. Organic zirconium or titanium salts may be employed. An exemplary crosslinking agent is ammonium zirconium carbonate (AZC), for example BACOTE 20 supplied by MEL. Further exemplary crosslinking agents include titanium ammonium lactate, for example ORGATIX TC-300, triethanolamine titanate, for example ORGATIX TC-400 supplied by Mazimuto Fine Chemical Limited. Zinc and boron containing crosslinking agents may also be employed.

[0040] The crosslinking agents may be supplied as solutions. For example, AZC may be supplied in an 18 wt % aqueous solution.

[0041] The amounts referred to below are by wet weight of the ingredient.

[0042] The amount of the crosslinking agent may be 0.05 wt % to 1.0 wt %, alternatively 0.15 wt % to 0.35 wt %.

[0043] The emulsifier may be selected from fatty acid esters of saturated or unsaturated C.sub.3 to C.sub.22 carboxylic acids, alternatively stearates, oleates and laurates.

[0044] The amount of the emulsifier may be 1.5 wt % to 10 wt %, alternatively 2 wt % to 4 wt % and alternatively between 2.2 wt % to 3.0 wt %.

[0045] The plasticiser may be selected from: castor oil, butyl ricinoleate, sebacates, for example dibutyl sebacate, benzoates, for example glyceryl benzoate or glyceryl tribenzoate, adipates and phthalates. The amount of the plasticiser may be 5 wt % to 25 wt %, alternatively 5 wt % to 15 wt %.

[0046] The amount of water used may be from 40 wt % to 75 wt %, more preferably from 50 wt % to 60 wt %.

[0047] Optional further ingredients which may be employed include: water based biocidal agents, natural thickeners such as xanthan gum, cellulose ether, carboxy methyl cellulose, guar, polysaccharides. Also associative thickeners such fully hydrolysed polyacrylic acid, polyurethane (HEUR) and HASE thickeners can be incorporated to control rheology, sedimentation and storage stability.

[0048] According to a second aspect of the present invention, a method of preparation of a stable aqueous film forming dispersion comprises the steps of: heating a mixture comprising:

[0049] a polymer selected from the group consisting of: polyvinyl butyral, polyvinyl acetal, ethylene vinyl acetate, vinyl acetate and mixtures thereof:

[0050] a plasticiser;

[0051] an emulsifier; and

[0052] water,

[0053] with stirring under pressure at a temperature between 110° C. and 150° C. to form a water-in-oil emulsion plasticised polymer melt;

[0054] adding water to the melt to cause phase inversion to form an oil-in-water emulsion;

[0055] cooling the oil-in-water emulsion to a temperature between 0° C. and 40° C.;

[0056] adding a water soluble organic metallic crosslinking agent and any optional further additives to form a stable aqueous film forming dispersion.

[0057] The ingredients of the composition may be as disclosed in accordance with the first aspect of the present invention

[0058] The dispersion may be solid at ambient temperatures.

[0059] The preferred mixing temperature is in the range 125° C. to 135° C.

[0060] The ingredients may be mixed in a pressure vessel to form the emulsion. Alternatively an extruder may be used.

[0061] A preferred method using an extruder is disclosed in EP 1971471, the disclosure of which is incorporated into this specification for all purposes by reference.

[0062] An exemplary procedure may comprise the following steps: [0063] a) Plasticiser and initial water to a heated and pressure rated mixing vessel equipped with a suitable agitator. [0064] b) Add PVB resin and stir contents for 1 hour. [0065] c) Then add required alkali neutralised fatty acid soap to the mixture and seal the mixing vessel. Stir contents at 300 rpm for 1.5 hours and heat product to temperature of between 110° C. to 150° C. or more preferably between 125 ° C. to 135° C. to fully combine the contents and form a water-in-oil emulsion plasticised polymer melt. [0066] d) Then slowly add first 12.5% of hot water (80 ° C. to 95° C.) to the polymer melt over 20-25 minutes to initiate the phase inversion process of converting the ‘water-in-oil’ emulsion to an ‘oil-in-water’. This inversion process may be characterised by a significant or sharp rise in viscosity of the emulsion. Beyond the phase inversion point the remaining hot water can be added quickly and will result in a steady reduction in the viscosity of the resulting PVB emulsion. [0067] e) Once all water has been added the contents of the vessel are cooled to below 40° C. at which point any further additives (e.g. thickener, biocide) can be added to the emulsion. [0068] f) An aqueous solution of ammonium zirconium carbonate or other suitable water soluble organometallic cross-linking agent is then added. [0069] g) The final PVB emulsion may be discharged via a suitable filtration system to remove any aggregates formed during the pressurised emulsification process.

[0070] According to a third aspect of the present invention there is provided a film or coating formed by removal of water from a dispersion in accordance with the first aspect of this invention or made by the method of the second aspect of this invention.

[0071] Films in accordance with this invention may be formed at ambient temperatures and may comprise coherent tack free films without outstanding hydrophobicity. The films may be resistant to water penetration when subject to wet or high humidity environments.

[0072] The films are suitable for formation of coatings and adhesives for temporary or permanent protection of or adhesion to substrates such as metals, glass, polymers and wood.

[0073] The dispersions are stable at ambient or working temperatures used for storage for water based dispersions. The dispersions provide a single component system which can be stored for a long period, for example six months, before activation by drying.

[0074] Without wishing to be bound by theory, it is believed that the crosslinking agent serves to crosslink residual PVB hydroxyl functionality and carboxylic acid functionality of the polymer and emulsifier respectively, the crosslinking being initiated by the evaporation of water and loss of ammonia during drying of the film. The cross-linked emulsifier and PVB may form a hydrophobic barrier significantly reducing the water sensitivity of the dried film without the need for heat or secondary cross-linking. This significantly increases the water resistivity of the dried film or coating when subjected to water immersion, rain or very high humidity environments.

[0075] Without the addition of the water soluble organometallic cross-linker the emulsifier and hydroxyl functionality on PVB resin may remain essentially unchanged increasing the hydrophilicity and leading to high water permeability of the resultant film or coating.

[0076] The crosslinkable and plasticised PVB dispersions of this invention are suitable for the production of temporary protective coatings for use in the automotive, marine, construction coating sectors. Examples of specific applications include temporary protective or decorative coatings for spray booths, cars, aerospace, advertising media and the like.

[0077] Percentages and other quantities referred to in the specification are by weight unless indicated otherwise. Amounts are selected from any ranges quoted to total 100%.

[0078] The invention is further described by means of example, but not in any limitative sense.

EXAMPLE 1

[0079] A dispersion was made using the following ingredients:

TABLE-US-00001 wt/kg Polymer G 15.51 Mowital B20H 15.51 Castor oil No 1 13.31 Hot water 38.29 Oleic acid 2.09 50% Potassium hydroxide 0.41 33% Ammonia solution 0.19 Initial water 10.37 Acticide MBL 0.2 1% Xanthan gum solution 3.8 Ammonium zirconium 0.32 carbonate (AZC) Total 100 [0080] The following procedure was used: [0081] 1. Add castor oil and initial water to the pressure vessel. [0082] 2. Add Polymer G and Mowital B20H and stir at 200 rpm. Continue to stir for 1 hour in total. [0083] 3. Add pre reacted oleic acid, potassium hydroxide and ammonia and heat to 125-130′C [0084] 4. Stir at 300 rpm for 1.5 hours. [0085] 5. Add first 12.5% of water addition over 20-25 minutes and the remainder over 10 mins. [0086] 6. Once below 40° C. add Acticide MBL biocide, xanthan gum solution [0087] 7. Add the required dosage of ammonium zirconium carbonate to one half of the sample. The second half was used for baseline evaluation.

EXAMPLE 1a

A Dispersion was Made Using the Following Ingredients:

[0088]

TABLE-US-00002 Trade name Chemical name wt (kg) Polymer G Polyvinyl butyral 15.51 Mowital B20H Polyvinyl butyral 15.51 Castor Oil — 13.31 Antioxidant 1076 Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate 0.5 Initial Water — 10.37 Oleic Acid — 2.09 50% Potassium Hydroxide — 0.41 Solution 33% Ammonia Solution — 0.19 Hot Water — 34.91 1% Xanthan.gum Solution — 7 Acticide MBL Mixture of 2-methyl-4-isothiazolin-3-one, 0.2 1,2-benzisothiazolin-3-one, and 2-bromo-2- nitro-propane-1,3-diol Total 100 [0089] The following procedure was used: [0090] 1. Add castor oil and initial water to the pressure vessel. [0091] 2. Add Polymer G and Mowital B20H and stir at 200 rpm. Continue to stir for 1 hour in total. [0092] 3. Add pre reacted oleic acid, potassium hydroxide and ammonia and heat to 135° C. [0093] 4. Stir at 300 rpm for 1.5 hours. [0094] 5. Add first 12.5% of water addition over 20-25 minutes and the remainder over 10 mins. [0095] 6. Once below 40° C. add Acticide MBL biocide and xanthan gum solution

EXAMPLE 1b

Example 1a was Modified Using the Following Formulation:

[0096]

TABLE-US-00003 wt (kg) Example 1a 98.36 19.5% Ammonium Zirconium 1.64 Carbonate Solution Total 100 [0097] The following procedure was used: [0098] 1. Under mild high shear stirring, ammonium zirconium carbonate solution was added slowly, drop wise. [0099] 2. The mixture was stirred for 5 minutes once all AZC was added.

EXAMPLE 1a

Composition Without AZC

[0100] The properties of the composition were as follows [0101] Total Solids, %: 47.80 [0102] pH: 9.48 [0103] Particle size (d50), μm: 0.852

EXAMPLE 1b

Composition with 1.64 kg of a 19.5% AZC Solution (0.32 kg Active)

[0104] The properties of the composition were as follows [0105] Total Solids, %: 47.23 [0106] pH: 9.20 [0107] Particle size (d50), μm: 0.852

EXAMPLE 2a

A Dispersion was Made Using the Following Ingredients:

[0108]

TABLE-US-00004 Trade name Chemical name wt (kg) Mowital B75H Polyvinyl butyral 14.33 Mowital B60H Polyvinyl butyral 14.33 Castor Oil — 14.33 Antioxidant 1076 Octadecyl-3-(3,5-di-tert-butyl- 0.5 4-hydroxyphenyl)propionate Initial Water — 12.17 Oleic Acid — 2.09 50% Potassium Hydroxide — 0.83 Solution Hot Water — 34.22 1% Xanthan.gum Solution — 7 Acticide MBL Mixture of 2-methyl-4-isothiazolin- 0.2 3-one, 1,2-benzisothiazolin-3-one, and 2-bromo-2-nitro-propane- 1,3-diol Total 100

[0109] The following procedure was used: [0110] 1. Add castor oil and initial water to the pressure vessel. [0111] 2. Add Mowital B60H and Mowital B75H and stir at 200 rpm. Continue to stir for 1 hour in total. [0112] 3. Add pre reacted oleic acid and potassium hydroxide and heat to 135° C. [0113] 4. Stir at 300 rpm for 1.5 hours. [0114] 5. Add first 12.5% of water addition over 20-25 minutes and the remainder over 10 mins. [0115] 6. Once below 40° C. add Acticide MBL biocide, xanthan gum solution

EXAMPLE 2b

Example 2a was Modified Using the Following Formulation:

[0116]

TABLE-US-00005 wt (kg) Example 2a 97.44 19.5% Ammonium Zirconium 2.56 Carbonate Solution Total 100

[0117] The following procedure was used: [0118] 1. Under mild high shear stirring, ammonium zirconium carbonate solution was added slowly, drop wise. [0119] 2. The mixture was stirred for 5 minutes once all AZC was added.

EXAMPLE 2a

Composition Without AZC

[0120] The properties of the composition were as follows [0121] Total Solids, %: 46.6 [0122] pH: 9.43 [0123] Particle size (d50), μm: 2.546

EXAMPLE 2b

Composition with 2.56 kg of a 19.5% AZC Solution (0.5 kg Active)

[0124] The properties of the composition were as follows [0125] Total Solids, %: 46.3 [0126] pH: 9.16 [0127] Particle size (d50), μm: 2.546

EXAMPLE 3a

Reference Competitor A

[0128] A PVB emulsion derived from recovered plasticised PVB reclaimed from laminated glass stabilised with an emulsifier was used. [0129] The properties of the composition were as follows: [0130] Total solids, %=47% [0131] pH: 9.47 [0132] Particle size (d50), micron: 4.305

EXAMPLE 3b

Reference Competitor B

[0133] A PVB emulsion plasticised with castor oil (2:1) and emulsified using sodium sulphonate was used. [0134] The properties of the composition were as follows: [0135] Total Solids, %=42.44% [0136] pH=8.2 [0137] particle size (d50), micron=4.265

EXAMPLES 1 TO 3

Test Results

[0138] Method—Percentage water uptake
Pre-calculated quantities of each PVB emulsion were added to new aluminium weighing trays to give dry films with a thickness of 300 μm. These were dried for 72 hours at ambient temperature and on as flat as possible surface to ensure uniformity. Films were then cut in to shape and weighed. They were then placed in water for 5, 30, 60, 240 and 1440 minutes. After they had been immersed for the required time they were carefully dried of surface water and re-weighed. The results are shown in FIG. 1 and Table 1.

[0139] This was repeated with drying times of 24 hours and 24 hours+1 hour at 60° C. The results are shown in FIGS. 2 and 3 and Tables 2 and 3.

[0140] Percentages of water taken up after 72 hours at ambient temperatures were as shown in the table below:

TABLE-US-00006 TABLE 1 72 Hours Ambient Reference 5 30 60 240 1440 Example 1(a) 0.34% 1.82% 3.74% 13.98% 27.40% Example 1(b) 0.62% 1.50% 2.38% 9.00% 19.03% Example 2(a) 1.92% 8.79% 18.14% 40.17% 10.28% Example 2(b) 0.89% 4.19% 6.58% 20.79% 14.00% Example 3(a) 4.42% 16.46% 26.48% 100.60% 30.55% Example 3(b) 0.45% 1.33% 2.28% 24.25% 9.93% NOTE: The % water uptakes highlighted in bold indicated that the dried film was beginning to lose integrity and re-emulsify during water immersion.
Percentages of water taken up after 24 hours at ambient temperatures were as shown in Table 2 below:

TABLE-US-00007 TABLE 2 24 hours At Ambient Temperature: 24 hours Reference 5 30 60 240 1440 Example 1(a) 0.99% 3.76% 8.35% 24.24% 17.85% Example 1(b) 0.51% 1.37% 3.63% 6.95% 10.17% Example 2(a) 3.16% 13.15% 45.03% 38.31% 16.58% Example 2(b) 1.55% 4.83% 8.44% 16.35% 6.22% Example 3(a) 0.00% 1.43% 7.75% 21.98% 44.60% Example 3(b) 4.62% 23.26% 34.81% 21.11% 15.88%
Percentages of water taken up after 24 hours plus 1 hour stoving at 60° C. were as shown in Table 3 below:

TABLE-US-00008 TABLE 3 24 Hours at ambient temperature + 1 hour at 60° C. 24 hours + 1 hour 60′C Reference 5 30 60 240 1440 Example 1(a) 0.73% 0.95% 2.83% 5.63% 18.05% Example 1(b) 0.62% 1.31% 2.35% 7.77% 17.93% Example 2(a) 1.11% 4.30% 12.21% 32.05% 18.75% Example 2(b) 1.28% 2.67% 7.21% 15.70% 19.70% Example 3(a) 0.63% 0.99% 1.91% 4.48% 17.02% Example (3(b) 1.55% 4.57% 10.28% 30.83% 20.82%

[0141] Further experiments were carried out. The results are shown in the following FIGS. 4 to 9.

EXAMPLE 4a

A Dispersion was Made Using the Following Ingredients:

[0142]

TABLE-US-00009 Trade name Chemical name wt (kg) Polymer G Polyvinyl butyral 15.445 Mowital B20H Polyvinyl butyral 15.445 castor oil — 13.24 antioxidant 1076 Octadecyl-3-(3,5-di-tert-butyl- 0.5 4-hydroxyphenyl)propionate initial water — 10.37 Oleic Acid — 2.1 50% potassium hydroxide — 0.414 Solution 33% ammonia solution — 0.19 hot water — 35.096 1% Xanthan gum solution — 7 Acticide MBL Mixture of 2-methyl-4-isothiazolin- 0.2 3-one, 1,2-benzisothiazolin-3-one, and 2-bromo-2-nitro-propane- 1,3-diol Total 100

[0143] The following procedure was used: [0144] 8. Add castor oil and initial water to the pressure vessel. [0145] 9. Add Polymer G and Mowital B20H and stir at 200 rpm. Continue to stir for 1 hour in total. [0146] 10. Add pre reacted oleic acid, potassium hydroxide and ammonia and heat to 135° C. [0147] 11. Stir at 300 rpm for 1.5 hours. [0148] 12. Add first 12.5% of water addition over 20-25 minutes and the remainder over 10 mins. [0149] 13. Once below 40° C. add Acticide MBL biocide and xanthan gum solution

EXAMPLE 4b

Example 4a was Modified Using the Following Formulation:

[0150]

TABLE-US-00010 Ingredients % wt (kg) Example 4a 98.97 19.5% Ammonium Zirconium Solution 1.03 Total 100

[0151] The following procedure was used: [0152] 1. Under mild high shear stirring, ammonium zirconium carbonate (AZC) solution was added slowly, drop wise. [0153] 2. The mixture was stirred for 5 minutes once all AZC was added.

EXAMPLE 4a

Composition Without AZC

[0154] The properties of the composition were as follows [0155] Total Solids, %: 47.50 [0156] pH: 9.42 [0157] Particle size (d50), μm: 0.652

EXAMPLE 4b

Composition with 1.03 kg of a 19.5% AZC Solution (0.2 kg Active)

[0158] The properties of the composition were as follows [0159] Total Solids, %: 46.81 [0160] pH: 9.35 [0161] Particle size (d50)m μm: 0.652

EXAMPLE 5a

A Dispersion was Made Using the Following Ingredients:

[0162]

TABLE-US-00011 Trade name Chemical name wt (kg) Polymer G Polyvinyl butyral 15.445 Mowital B20H Polyvinyl butyral 15.445 Castor Oil — 13.24 Antioxidant 1076 Octadecyl-3-(3,5-di-tert-butyl- 0.5 4-hydroxyphenyl)propionate Initial Water — 10.37 Stearic Acid — 2.12 50% Potassium Hydroxide — 0.414 Solution 33% Ammonium Solution — 0.19 Hot Water — 35.076 1% Xanthan.gum Solution — 7 Acticide MBL Mixture of 2-methyl-4-isothiazolin- 0.2 3-one, 1,2-benzisothiazolin-3-one, and 2-bromo-2-nitro-propane- 1,3-diol Total 100

[0163] The following procedure was used: [0164] 1. Add castor oil and initial water to the pressure vessel. [0165] 2. Add Polymer G and Mowital B20H and stir at 200 rpm. Continue to stir for 1 hour in total. [0166] 3. Add pre reacted stearic acid, potassium hydroxide and ammonia and heat to 135′C [0167] 4. Stir at 300 rpm for 1.5 hours. [0168] 5. Add first 12.5% of water addition over 20-25 minutes and the remainder over 10 mins. [0169] 6. Once below 40′C add Acticide MBL biocide, xanthan gum solution

EXAMPLE 5b

Example 5a was Modified Using the Following Formulation:

[0170]

TABLE-US-00012 wt (kg) Example 5a 98.97 19.5% Ammonium Zirconium Solution 1.03 Total 100

[0171] The following procedure was used: [0172] 1. Under mild high shear stirring, ammonium zirconium carbonate solution was added slowly, drop wise. [0173] 2. The mixture was stirred for 5 minutes once all AZC was added.

EXAMPLE 5a

Composition Without AZC

[0174] The properties of the composition were as follows [0175] Total Solids, %: 47.12 [0176] pH: 9.41 [0177] Particle size (d50), μm: 1.405

EXAMPLE 5b

Composition with 1.03 kg of a 19.5% AZC Solution (0.2 kg Active)

[0178] The properties of the composition were as follows [0179] Total Solids, %: 46.35 [0180] pH: 9.27 [0181] Particle size (d50), μm: 1.405

EXAMPLE 6a

A Dispersion was Made Using the Following Ingredients:

[0182]

TABLE-US-00013 Chemical name wt (kg) Polymer G Polyvinyl butyral 15.445 Mowital B20H Polyvinyl butyral 15.445 Castor Oil — 13.24 Antioxidant 1076 Octadecyl-3-(3,5-di-tert-butyl- 0.5 4-hydroxyphenyl)propionate Initial Water — 10.37 TOFA 2 (Tall oil fatty — 2.1 acids) 50% Potassium Hydroxide — 0.414 Solution 33% Ammonium Solution — 0.19 Hot Water — 35.096 1% Xanthan gum Solution — 7 Acticide MBL Mixture of 2-methyl-4-isothiazolin- 0.2 3-one, 1,2-benzisothiazolin-3-one, and 2-bromo-2-nitro-propane- 1,3-diol Total 100

[0183] The following procedure was used: [0184] 1. Add castor oil and initial water to the pressure vessel. [0185] 2. Add Polymer G and Mowital B20H and stir at 200 rpm. Continue to stir for 1 hour in total. [0186] 3. Add pre reacted TOFA, potassium hydroxide and ammonia and heat to 115-120° C. [0187] 4. Stir at 300 rpm for 1.5 hours. [0188] 5. Add first 12.5% of water addition over 20-25 minutes and the remainder over 10 mins. [0189] 6. Once below 40° C. add Acticide MBL biocide, xanthan gum solution

EXAMPLE 6b

Example 6a was Modified Using the Following Formulation:

[0190]

TABLE-US-00014 wt (kg) Example 6a 98.97 19.5% Ammonium Zirconium Solution 1.03 Total 100

[0191] The following procedure was used: [0192] 1. Under mild high shear stirring, ammonium zirconium carbonate solution was added slowly, drop wise. [0193] 2. The mixture was stirred for 5 minutes once all AZC was added.

EXAMPLE 6a

Composition Without AZC

[0194] The properties of the composition were as follows [0195] Total Solids, %: 47.34 [0196] pH: 9.27 [0197] Particle size (d50), μm: 1.071

EXAMPLE 6b

Composition with 1.03 kg of a 19.5% AZC Solution (0.2 kg Active)

[0198] The properties of the composition were as follows [0199] Total Solids, %: 46.61 [0200] pH: 9.21 [0201] Particle size (d50), μm: 1.071 [0202] Percentages of water taken up after 72 hours at ambient temperatures were as shown in Table 4:

TABLE-US-00015 TABLE 4 72 Hours Ambient Reference 5 30 60 240 1440 Example 4a 0.83% 2.29% 3.40% 9.54% 26.72% Example 4b 0.66% 1.73% 2.48% 7.88% 21.89% Example 5a 0.65% 1.99% 2.84% 5.21% 8.31% Example 5b 0.61% 1.57% 2.02% 3.62% 5.63% Example 6a 1.09% 3.36% 5.39% 8.22% 7.94% Example 6b 1.59% 4.70% 6.66% 12.63% 7.19% Competitor A 4.37% 31.96% 49.34%* 114.62%* 130.58%* Note: The % water uptakes highlighted in bold indicated that the dried film was beginning to lose integrity and re-emulsify during water immersion. Those highlighted in bold with a * showed loss of integrity and swelling/blistering due to pockets of water.

TABLE-US-00016 TABLE 5 Percentages of water taken up after 24 hours at ambient temperatures 24 Hours Ambient Reference 5 30 60 240 1440 Example 4a 0.38% 3.25% 5.14% 10.86% 28.64% Example 4b 0.25% 1.98% 3.13% 8.45% 20.49% Example 5a 0.95% 3.42% 4.48% 6.39% 10.90% Example 5b 0.25% 1.32% 1.70% 2.72% 5.51% Example 6a 1.16% 5.63% 7.63% 14.46% 18.91% Example 6b 0.86% 5.32% 7.08% 10.34% 16.09% Competitor A 4.10% 100.82%* 142.53%* 79.88%* 232.25%*

TABLE-US-00017 TABLE 6 Percentages of water taken up after 24 hours plus 1 hour stoving at 60° C. 24 Hours Ambient + 1 Hour Stoving At 60° C. Time 5 30 60 240 1440 Example 4a 1.33% 2.51% 3.33% 8.01% 21.04% Example 4b 0.89% 2.68% 3.58% 8.32% 19.42% Example 5a 0.46% 2.06% 9.28% 10.97% 6.74% Example 5b 0.56% 1.57% 2.16% 5.07% 9.02% Example 6a 1.17% 5.22% 6.53% 11.97% 12.98% Example 6b 1.46% 3.94% 5.51% 14.49% 7.56% Competitor A 0.99% 10.43% 19.75% 31.86% 73.75%