Vesiculated polymer particles

According to the invention, the blister polymer particles include particulate solids and, on their surface, have long chain aliphatic chemical groups and / or sterically hindered, branched chain chemical groups.

In one form of the invention, the chemical groups are hydrophobic and contain organic compounds having at least one polymerizable carbon-carbon double bond with linear, branched or cyclic moieties having at least fourteen, but not more than twenty-five, carbon atoms; The following include, but are not limited to:

Octadecene; Loryl methacrylate; Acrylated castor oil; Acrylated ricinoleic acid;

Methacrylated ricinoleic acid; Soybean Oil; Unsaturated fatty acids such as oleic acid, tallow fatty acid; Unsaturated fatty alcohols such as Oleyl alcohol, pentadeca-12-en-1-ol .; oleamide; Triglycerides, for example, tall oil, ting oil; Ethyleneic unsaturated urethanes; Acrylic unsaturated urethanes; Air-drying short oil alkyds; Alkyl and aryl esters of maleic anhydride and mixtures thereof.

These monomers are substantially more hydrophobic than typical monomers used in the prior art, for example, methyl methacrylate, ethyl acrylate, acrylonitrile and vinyl toluene.

In this description, the term compound may refer to groups encompassed in the polymer particles or groups applied to the surface or surface portions of the polymer particles.

According to a second aspect of the invention, a raw material composition for the manufacture of blister particles comprises a carboxylic acid functional, free-radical polymerizable polyester resin, a co-reactive diluent monomer, and a modifying comonomer, the modifying comonomer, at least fourteen, but at least one polymerizable carbon-carbon double bond having linear, branched or cyclic moieties having not more than twenty-five carbon atoms, these comonomers include, but are not limited to:

Loryl methacrylate; Acrylated castor oil; Acrylated ricinoleic acid; Methacrylated ricinoleic acid; Soybean Oil; Unsaturated fatty acids such as oleic acid, tallow fatty acid; Unsaturated fatty alcohols such as Oleyl alcohol, pentadeca-12-en-1-ol .; oleamide; Triglycerides, for example, tall oil, ting oil; Ethyleneic unsaturated urethanes; Acrylic unsaturated urethanes; Air-drying short oil alkyds; Alkyl and aryl esters of maleic anhydride and mixtures thereof.

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The modifying comonomer may comprise from 3 to 20% by weight of the added reactive diluent monomer and preferably from 5 to 9% by weight of the added diluent monomer. These amounts exclude diluent monomer present in the polyester resin.

Suitable diluent comonomers include ethylenic, acrylic and methacrylic functional monomers such as styrene, butyl acrylate, methyl methacrylate, and preferably styrene.

In one form, the polyester resin composition comprises:

Propylene glycol 30.35%

Phthalic anhydride 12.96%

Maleic anhydride 25.75%

Styrene 30.75% inhibitor (10% solution) 0.18%

TOTAL 100.00

According to a third aspect of the invention, a method of manufacturing blister particles comprises the following steps:

- pre-dispersing the pigment particles in a polyester;

- the pre-dispersed pigment-polyester is dissolved in a suitable monomer in the presence of a water-soluble base;

forming a stable emulsion of droplets of a solution of the pigment-polyester and monomer (oil phase) in water in the form of a pre-dispersion;

a hydrophobic monomer is added, and the polyester and copolymerizable monomer are polymerized to form granules of matt, crosslinked blister particles dispersed in water, the particles including hydrophobic groups attached to their surface.

The delayed addition of the hydrophobic (modifying) monomer at a point at which a stable emulsion is formed results in the maintenance of the particle size of the blister particles produced as a result of mixing during the emulsification.

In one form, the base may comprise a polyamine, for example diethylenetriamine.

When the polyester is emulsified in water, particles of various sizes can be manufactured using different mixers with different mixing densities. In one form of the invention, suitably designed equipment, for example homogenizers, can be used to control pressure, temperature and residence time. Particle size and particle size

55218 chemical control of the dispersion is also accomplished by incorporation of long chain aliphates or sterically hindered, branched, chain comonomers.

It has been found that it is preferable to add these materials at a later stage during emulsification of the organic phase in the water phase, since the majority of these monomers or macro-monomers coalesce the average particle size when incorporated into the blister polymer particles. This minimized the effect on particle size. However, a coarser particle size variety may be used to impart particular effects to the dye, for example, in terms of texture.

When incorporated into paint systems, modified blister polymer particles have the effect of improving water resistance, abrasion resistance, whiteness and opacity.

EXAMPLES

The following examples are intended to illustrate the invention but not to limit the scope of the invention.

Example 1

The following blister polymer particles were synthesized according to the prior art.

<td colspan="2">Parts by weight</td>

<td>Phase 1</td><td></td>

<td>Polyester</td><td> 14.99</td>

<td>Titanium Dioxide</td><td> 0.86</td>

<td>styrene</td><td> 6.54</td>

<td>Diethylene Triamine</td><td> 0.21</td>

<td>Stage 2</td><td></td>

<td>Polyvinyl alcohol solution (10%)</td><td> 13.28</td>

<td>Hydroxy Ethyl cellulose solution (2.5%)</td><td> 10.45</td>

<td>That</td><td> 52.92</td>

<td>Diethylene Triamen</td><td> 0.06</td>

<td>Phase 3</td><td></td>

<td>That</td><td> 0.21</td>

<td>Ferros Sulfate</td><td> 0.01</td>

<td>Sumene Hydroperoxide</td><td> 0.12</td>

<td>Stage 4 Bakteriasid</td><td> 0.35</td>

<td colspan="2"> 100.00</td>

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Procedure

one. Titanium dioxide is dispersed in high speed polyester in a high shear stress mixer.

2nd. 1) Styrene and Diethienine Triamine are added to the material of step 1).

3. Stage 2 is prepared in a separate vessel at low speed.

4. The Stage 1 material (organic phase) is added to the high speed Stage 2 material in a high shear stress mixer and mixed until the desired particle size of the organic phase is obtained.

5. Subsequently, Stage 3 is first added after pre-mixing and adding Ferros Sulfate and water. This addition is followed by the addition of Sumene Hydroperoxide.

6. The mixer is stopped and the product is allowed to cure overnight without being touched.

7. The blister particles are then mixed until homogeneous and a suitable bacteriacid is added.

A viscous white dispersion of the crosslinked polymer particles in water is obtained 15, which forms non-film forming particles upon drying, such that a plurality of air voids are present.

The average particle size will vary depending on the mixing density applied when the Stage 1 - Stage 2 agents are added.

Example 2

As in Example 1, however, 0.1% of Styrene was replaced with Loryl Methacrylate. The mixing conditions are as in Example 1.

Example 3

As in Example 1, however, 3% of Styrene was replaced with Loryl Methacrylate. The mixing conditions are as in Example 1.

Example 4

As in Example 1, but 5% of Styrene was replaced with Loryl Methacrylate. The mixing conditions are as in Example 1.

Example 5

As in Example 1, but 7% of Styrene was replaced with Loryl Methacrylate. Mixing 30 conditions are as in Example 1.

Example 6

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As in Example 1, but 9% of Styrene was replaced with Loryl Methacrylate. The mixing conditions are as in Example I.

Example 7

As in Example 1, but 20% of Styrene was replaced with Loryl Methacrylate. Mixing 5 conditions are as in Example 1.

Example 8

The blister particles produced in the above examples 1-7 were measured for the following properties:

one. Total solids content using a Mettler HR73 halogen moisture analyzer.

2nd. Viscosity using a Brookfield LVT viscometer.

3. PH using a Metrohm 744 pH meter.

4. Specific weight using a Sheen 100cc per gallon weight dish.

5. Leneta form opacity using 2A opacity schemes and Sheen micropak reflectometer.

6. Whiteness using BYk-Gardner color-appearance spectrophotometer.

7. Average particle size using a scanning electron microscope (Topcon and

Scion image analysis software).

The results are as follows:

Bubbly Particles Manufactured in Variable Shear Stress Cowles Mixer

<td>LME %</td><td>Participating is, %</td><td>Viscosity, cPS</td><td>PHA</td><td>SG</td><td>opaqueness</td><td>Whiteness</td><td>Cover. Particle Size, micron</td>

<td> 0</td><td> 23.50</td><td> 800</td><td> 6.78</td><td> 1.043</td><td> 0.93</td><td> 94.0</td><td> 5.6</td>

<td> 0.1</td><td> 23.80</td><td> 610</td><td> 6.66</td><td> 1.044</td><td> 0.96</td><td> 96.7</td><td> 6.1</td>

<td> 3</td><td> 23.90</td><td> 1200</td><td> 6.50</td><td> 1.044</td><td> 0.96</td><td> 96.1</td><td> 6.9</td>

<td> 5</td><td> 23.63</td><td> 1250</td><td> 6.55</td><td> 1.046</td><td> 0.95</td><td> 96.4</td><td> 7.5</td>

<td> 7</td><td> 23.7</td><td> 3720</td><td> 6.74</td><td> 1.042</td><td> 0.96</td><td> 97.0</td><td> 8.3</td>

<td> 9</td><td> 23.46</td><td> 3900</td><td> 6.75</td><td> 1.044</td><td> 0.95</td><td> 95.4</td><td> 16.0</td>

<td> 20</td><td> 23.67</td><td> 14800</td><td> 6.73</td><td> 1.033</td><td> 0.88</td><td> 94.5</td><td> 36.5</td>

The improvement in opacity and whiteness as well as the effect of increasing particle size were clearly visualized. ,

Example 9

The blister polymer particles from Examples 1-7 were formulated into the following mixture to produce the water-based emulsion paint:

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<td>RAW MATERIAL</td><td>WEIGHT PART</td>

<td>Bubbly particles</td><td> 77.5</td>

<td>Styrene acrylic emulsion polymer</td><td> 9.7</td>

<td>Coupling agent</td><td> 1.1</td>

<td>Ammonia (1: 1 dilution with water)</td><td> 1</td>

<td>Aqueous dispersion of titanium dioxide</td><td> 9.7</td>

<td>Thickening agent</td><td> 1</td>

In this example, the dyes obtained using the blister particles from Examples 1-7 were tested for wet scratch resistance and the following results were recorded:

one. Dye using Blister Particles from Example 1 = 20 cycles

2nd. Dye using Bubbly Particles from Example 2 = 120 cycles

3. Dye using Bubbly Particles from Example 3 = 500 cycles

4. Dye using Bubbly Particles from Example 4 = 1100 cycles

5. Paint using Bubbly Particles from Example 5 = 1500 cycles

6. Dye using Blister Particles from Example 6 = 900 cycles

7. Dye using Blister Particles from Example 7 = 600 cycles.

<img file="TR200501136T2_D0001.tif" />

The higher wet scratch cycle indicates better scratch and abrasion resistance in the final paint. The results confirm the improvements in water and scratch resistance obtained by using the compositions of the present invention in paints and coatings.

Example 10

Example 4 was repeated using Octadecene instead of Loryl Methacrylate. The mixing conditions were as in Example 1.

Example 11

Example 4 was repeated 20 using Acrylated Methyl Ricinolate instead of Loryl Methacrylate. The mixing conditions were as in Example 1.

Example 12

Example 4 was repeated using Methacrylated Risinolate instead of Loryl Methacrylate. The mixing conditions were as in Example 1.

Example 13

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The blister polymer particles from Examples 10, 11 and 12 were measured for properties as in Example 8 above.

The results are as follows:

Bubbly Particles Manufactured in Variable Shear Stress Cowles Mixer

<td>LME %</td><td>Participating is, %</td><td>Viscosity, cPS</td><td>PHA</td><td>SG</td><td>opaqueness</td><td>Whiteness</td><td>Cover. Particle Size, micron</td>

<td> 10</td><td> 23.39</td><td> 10000</td><td> 6.56</td><td> 1.045</td><td> 0.95</td><td> 95.0</td><td> 17</td>

<td> 11</td><td> 23.48</td><td> 1800</td><td> 6.72</td><td> 1.043</td><td> 0.96</td><td> 95.4</td><td> 9</td>

<td> 12</td><td> 23.50</td><td> 1900</td><td> 6.47</td><td> 1.045</td><td> 0.96</td><td> 95.2</td><td> 9</td>

Example 14

The blister polymer particles from Examples 10, 11 and 12 were formulated as water-based paints as in Example 9 and tested for wet scratch resistance.

one. Dye using blister particles from Example 1 = 20 cycles.

2nd. Dye using blister particles from Example 10 = 500 cycles.

3. Dye using blister particles from Example 11 = 1000 cycles.

4. Dye using blister particles from Example 12 = 1200 cycles.

The results confirm the improvements in water and scratch resistance obtained by using the compositions of the present invention in paints and coatings.

Example 15

Water resistance and whiteness of paint containing:

Blister particles synthesized using known technology (Example 1).

The bubbly particles synthesized using the technology of this patent (Example 4) were compared. The paint is a medium quality paint and is suitable for both internal and external use. The following results were obtained:

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<td>Paint Bubbly Particle supply</td><td>to (Example 1)</td><td>B (Example 4)</td>

<td>Water resistance</td><td></td><td></td>

<td>Water droplet method ⁽¹⁾</td><td>5 min</td><td>10 min.</td>

<td>Lak Wet wear resistance⁽²⁾</td><td>1280 cycles</td><td>2198 cycles</td>

<td>Color D10 ° (against Std)⁽³⁾</td><td></td><td></td>

<td>L</td><td>-0.28 D</td><td>-0.51 D</td>

<td>to</td><td>- 0.06 G</td><td>-0.10G</td>

<td>B</td><td>1.09 Y</td><td>0.43Y</td>

<td>DE CMC</td><td> 1.41</td><td> 0.63</td>

(1) Water resistance was achieved by subjecting a dried paint film to water droplets on the surface of the paint at ambient temperature for 24 hours. The time taken for the paint to soften or bubble in contact with water droplets was recorded. The longer the time, the better the water resistance. The experiment was stopped after 10 minutes.

(2) Wet wear resistance is made by the attached method. The higher the number of cycles, the better the wet wear resistance.

(3) The color was measured on a color computer and compared with the dye containing the blister particles from example 1.

If positive, L indicates light difference and negative indicates dark difference. Paint B is slightly darker than Paint A.

If A is positive, it indicates redness difference and if negative, it indicates greenery difference. Paint B is slightly greener than Paint A.

If B value is positive, it shows the difference in jaundice and if it is negative, it shows the difference in blue. Paint B is less yellow than Paint A and is therefore whiter.

DE CMC is the difference in color as a whole. Paint B has a lower color change as a whole than Paint A.

Example 16

Blister particles (ie, Examples 1 and 4) are formulated into the following water-based dyes:

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- Medium quality indoor / outdoor paint.

- High quality interior matt paint

- Effect paint.

The properties of the dyes were evaluated.

Below are the dye formulations and test results:

Example 17

The blister particles were synthesized as in Example 1 and Example 4.

The blister particles were applied to a black and white opacity scheme by means of a 200mm draw bar.

The opacity (ie wiping strength) was measured on the black and white portions of the opacity scheme by a reflectometer. The resulting reflection measurement on white is divided by the reflection measurement on black.

The results are as follows:

<td></td><td>Example 1</td><td>Example 4</td>

<td>opaqueness</td><td> 0.93</td><td> 0.95</td>

The higher the number, the greater the erasure power of the bubble grain.

High Quality Matt Indoor / Outdoor Paint

<td></td><td>Paint A</td><td>Paint B</td>

<td>That</td><td> 28.11</td><td> 28.11</td>

<td>Dispensing agent</td><td> 0.24</td><td> 0.24</td>

<td>Titanium dioxide</td><td> 7.90</td><td> 7.90</td>

<td>Calcium carbonate (2 microns)</td><td> 21.82</td><td> 21.82</td>

<td>Calcium carbonate (5 microns)</td><td> 8.11</td><td> 8.11</td>

<td>Propylene glycol</td><td> 1.02</td><td> 1.02</td>

<td>Anionic surfactant</td><td> 0.09</td><td> 0.09</td>

<td>Foam Receiver</td><td> 0.31</td><td> 0.31</td>

<td>Hydroxy ethyl cellulose</td><td> 0.33</td><td> 0.33</td>

<td>Ammonia</td><td> 0.11</td><td> 0.11</td>

<td>Styrene / Acrylic Emulsion (50% solid)</td><td> 17.20</td><td> 17.20</td>

<td>Coupling agent</td><td> 1.66</td><td> 1.66</td>

<td>Bakteriasid</td><td> 0.21</td><td> 0.21</td>

<td>Bubbly particles (Example 1)</td><td> 12.91 .</td><td> -</td>

<td>Bubbly particles (Example 2)</td><td> -</td><td> 12.91</td>

<td>TOTAL</td><td> 100.0</td><td> 100.0</td>

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RESULTS

<td></td><td>Paint A</td><td>Paint B</td>

<td>Water resistance tZl Water droplet method</td><td> 8</td><td>¹⁰</td>

<td>Lak Wet wear resistance</td><td> &gt; 10,000</td><td> &gt; 10,000</td>

<td>opaqueness</td><td> 0.88</td><td> 0.92</td>

<td>Whiteness⁽¹⁾</td><td> 79.57</td><td> 81.06</td>

Note: Dye B is more water-resistant, higher opacity and whiter than Dye A.

(1) Whiteness was measured on a color computer. The higher the number, the more white the paint is.

High Quality Matte Interior Paint

<td></td><td>Paint A</td><td>Paint B</td>

<td>1. Titanium dioxide dispersion</td><td> 21.32</td><td> 21.32</td>

<td>2. Talc dispersion</td><td> 19.07</td><td> 19.07</td>

<td>3. Thickening agent</td><td> 0.29</td><td> 0.29</td>

<td>4. Water</td><td> 2.02</td><td> 2.02</td>

<td>5. Ammonia</td><td> 0.24</td><td> 0.24</td>

<td>6. Propylene glycol</td><td> 0.77</td><td> 0.77</td>

<td>7. Binding agent</td><td> 1.345</td><td> 1.345</td>

<td>8. Foam receiver</td><td> 0.25</td><td> 0.25</td>

<td>9. Dispensing agent</td><td> 0.19</td><td> 0.19</td>

<td>10. Bacteriacid</td><td> 0.10</td><td> 0.10</td>

<td>11. Pure acrylic emulsion (48% solid)</td><td> 39.55</td><td> 39.55</td>

<td>12. Thickening agent (for low cutting)</td><td> 0.15</td><td> 0.15</td>

<td>13. Thickening agent (for high shear)</td><td> 0.29</td><td> 0.29</td>

<td>14. Water</td><td> 2.95</td><td> 2.95</td>

<td>15. Bubbly particles⁰’</td><td> 11.51</td><td> -</td>

<td>16. Bubbly particles⁽²⁾</td><td> -</td><td> 11.51</td>

<td>TOTAL</td><td> 100.0</td><td> 100.0</td>

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RESULTS

<td></td><td>Paint A</td><td>Paint B</td>

<td>Water resistance E] Water droplet method</td><td> 8</td><td> 10</td>

<td>Wet wear resistance of hand</td><td> &gt; 10,000</td><td> &gt; 10,000</td>

<td>opaqueness</td><td> 92.8</td><td> 95.1</td>

<td>Whiteness ⁽¹⁾</td><td> 78.23</td><td> 82.14</td>

Note: Paint B is more water resistant, higher opaque and whiter than Paint A.

(1) The bubbly particles were manufactured to an average particle size of 25 microns by adjusting the agitation rate and to the particle size of Example 1.

(2) Bubbly particles were manufactured at a particle size of 25 microns and the particle size of Example 4.

Effect Paint

<td></td><td>Paint A</td><td>Paint B</td>

<td>1. Water</td><td> 6.07</td><td> 6.07</td>

<td>2. Propylene glycol</td><td> 1.79</td><td> 1.79</td>

<td>3. Dispensing agent</td><td> 0.11</td><td> 0.11</td>

<td>4. Surfactant</td><td> 0.18</td><td> 0.18</td>

<td>5. Foam receiver</td><td> 0.09</td><td> 0.09</td>

<td>6. Bacteriacid</td><td> 0.05</td><td> 0.05</td>

<td>7. Ammonia</td><td> 0.10</td><td> 0.10</td>

<td>8. Hydroxy ethyl cellulose</td><td> 0.05</td><td> 0.05</td>

<td>9. Pure acrylic emulsion (48% solid)</td><td> 47.04</td><td> 47.04</td>

<td>10. Binding agent</td><td> 2.09</td><td> 2.09</td>

<td>11. Bubbly particles^(1&gt;</td><td> 39.16</td><td> -</td>

<td>12. Bubbly particles⁽²⁾</td><td> -</td><td> 39.116</td>

<td>13. Thickening agent</td><td> 1.23</td><td> 1.23</td>

<td>14. Water</td><td> 0.82</td><td> 0.82</td>

<td>15. Color tone substance (s)</td><td> 1.22</td><td> 1.22</td>

<td>TOTAL</td><td> 100.0</td><td> 100.0</td>

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RESULTS

<td></td><td>Paint A</td>

<td>Suede Effect⁽³⁾</td><td>No</td>

(1) Bubbly particles were manufactured to an average particle size of 25 microns by adjusting the agitation rate and to the particle size of Example 1.

(2) Bubbly particles were manufactured at an average particle size of 25 microns and the particle size of Example 4.

(3) Suede Effect is an effect that is imparted to a paint to impart a color texture effect.

Dye B has superior Suede Effect compared to Dye A since bubbly beads are more pronounced on the surface due to low water absorption.

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