# Patent

## Title
Exterior paint formulation

## Abstract

The present invention provides increased stain resistance, tannin blocking, adhesion, and various other properties. A composition in accordance with the principles of the present invention comprises at least two binders, nanoparticle pigment, and pigmentary titanium dioxide. In one embodiment, the present invention relates to a coating on a substrate wherein the coating has two binders, nanoparticle metal oxide pigment, and pigmentary titanium dioxide. Various additives may be included to formulate paint as known in the art.

## Background
CROSS REFERENCE TO RELATED PATENT APPLICATIONS
The present application is a divisional application of U.S. patent application Ser. No. 10/914,439, filed Aug. 9, 2004 and is incorporated herein by reference in its entirety.


FIELD OF THE INVENTION
The present invention relates to polymer resins. More particularly, the present invention relates to paints having a nanoparticle based pigment and a plurality of binders.
BACKGROUND OF THE INVENTION
Traditionally consumers have had to choose between the superior durability offered by latex paints and the superior hiding properties of oil-based paint. Conventional latex or emulsion paints require an underlying primer coat prior to their application to provide an adequate level of blocking and to prevent bleed-through, such as of tannins. In addition, many conventional latex paints require a primer coat to provide adequate adhesion and durability for specific applications. Often, even when a primer is applied, multiple coats of the prior art paints are required to prevent an alteration of color due to the presence of the primer or bleed through of dyes and pigments from the underlying substrate. In fact, multiple applications of prior art paint will not prevent bleed-through on substrates such as cedar since the dyes and pigments, such as tannins contained in the substrates, are often water soluble and diffuse through each layer of the latex paint.
Paint typically contains four essential ingredients, namely pigment, binder, liquid and additives. Any or all of these ingredients may be a single component or may comprise multiple items. Pigment provides color to paint and also makes paint opaque, and pigment is usually of mineral or organic origin although some pigments are artificially produced. Some pigments possess little or no bulk and must be fixed on a more solid, but at the same time transparent, substance or base. “Prime” pigments provide color and opacity (opaque coverage). The most common prime pigment is titanium dioxide, which is white and is used in latex and oil-based paints.
Traditionally, pigments have also added hiding properties to paint. Specialty or extender pigments may also be used and provide bulk to the paint at a low cost. The extender pigments are often chosen for their impact on properties like scrub resistance, stain resistance and chalk resistance. Alum or clay are frequently used for this purpose. These pigments are added to the paint to provide certain characteristics such as thickness, a certain level of gloss and durability. They are usually naturally occurring products which originally were in the earth and were mined and purified for use in paint. Such pigments as calcium carbonate, talc and clay are, for example, used extensively in paints.
The binder holds the pigment and also adheres it to a surface, and a binder composition may have more than one component. In latex paint, the latex resin is the binder. Most commonly in latex paint, the binder is 100% acrylic, vinyl acrylic (polyvinyl acetate), or styreneated acrylic. The pigment particles are insoluble and merely form a suspension in the binder. The binder “binds” the pigment into a tough, continuous film and as noted above helps the paint adhere to the surface. In addition, it has been found previously that the use of 100% acrylic binder provides for maximum adhesion when wet and also provides for resistance to blistering and peeling, resistance to mildew and dirt, and alkali resistance for paint applied over fresh masonry.
Liquids carry the pigment and binders, and this liquid is the part of the paint or coatings product which evaporates. The role of the fluid is to keep the paint in a fluid form for ease of application. Once applied to the surface it evaporates leaving a uniform film which then dries to form a protective coating. The liquid used is primarily determined by the solubility of the binder. In oil-based and alkyd paints, the liquid is typically a paint thinner, and in latex paints, the liquid is typically water. Traditionally, top quality paints have less liquid and more solids (i.e. pigment & binders) as measured by percent solid.
Additives are ingredients used at low levels to provide key properties, such as but not limited to: mildew resistance, better flow and leveling, and splatter resistance. Common additives used in conventional paint formulations include rheology modifiers, surfactants, defoamers, coalescents, and biocides. Other numerous additives are well-known in the art and may be utilized as required to formulate a paint having the desired properties.
Various techniques are known in the art for producing paints having various types of sheens, i.e. “shine” or gloss. For example, by incrementally increasing pigment levels and/or by using larger pigment particles, various gloss levels can be achieved including, but not limited to flat, satin, and semi-gloss. Pigment volume concentration (PVC) is often associated with the paint finish, although various finishes may have overlapping ranges of PVC. PVC is the unit volume of pigments as a percentage of the volume of pigments plus the volume of the binder. PVC represents the relationship between durability of the coating and the amount of pigment.
Thus, there is a need for a paint composition and method of making the same to replace the traditional role of a primer and topcoat system and which is capable of providing a coating having improved properties such as, tannin blocking, hiding power, stain removal, and corrosion resistance.
SUMMARY OF THE INVENTION
The present invention relates generally to a binder composition and a paint system with superior tannin blocking, stain removal, corrosion resistance, adhesion, and various other improved properties. The present invention preferably includes a two binder system with an inorganic nano-particle pigment and with a pigmentary titanium dioxide. In one embodiment, a paint composition in accordance with the principles of the present invention further includes additives for formulating paint. In another embodiment, the present invention relates to a coating on a substrate that provides improved coverage through the use of at least two binders, an inorganic nano-particle pigment and a pigmentary titanium dioxide.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a multi-axis property graph of the test results of paint of the present invention having a satin sheen and white base, as compared to commercially available exterior satin in a white base;
FIG. 2 depicts a multi-axis property graph of the test results of flat white base paint in accordance with the principles of the present invention, as compared to a commercially available exterior flat paint in a white base;
FIG. 3 illustrates a multi-axis property graph of the test results for semi-gloss white base paint of the present invention versus a commercially-available, exterior semi-gloss paint in a white base;
FIG. 4 illustrates a multi-axis property graph for a flat white base paint of the present invention versus a second commercially available exterior flat paint in a white base; and
FIG. 5 illustrates a multi-axis property graph for a satin white base paint of the present invention versus a second commercially-available, exterior satin paint in a white base.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is directed in part to a polymer composition within a paint system which replaces the traditional role of a primer and a topcoat with improved properties such as tannin blocking, stain removal, adhesion, and corrosion resistance. In one embodiment, the present invention relates to a composition having a first binder, a second binder, inorganic nanoparticle pigments, and in some cases a third binder. This composition can be used in a conventional paint formulation as known in the art.
Binders for use in the present invention include those prepared by conventionally known methods. Suitable binders include, but are not limited to, 100% acrylic resins and styreneated, acrylic resins as manufactured. Preferably, the first binder is a 100% acrylic resin designed to be used as a primer vehicle, and the second binder is a 100% acrylic resin designed to be used in top coating applications.
Pigments for use in the present invention may comprise any suitable pigments known in the art. In one embodiment, the pigments of the present invention are titanium oxide or zinc oxide but other suitable pigments include nepheline syenite, bentonite, and calcium carbonate. Preferably, the primary pigment is titanium dioxide, such as commercially available pigments.
Metal oxide nanoparticle materials for use in a preferred embodiment of the invention have an average particle size of about 20-150 nanometers, although some embodiments can employ average sizes outside this range. In one preferred embodiment, the nanoparticle material is a zinc oxide material having an average particle size of about 60 nm.
A paint can be prepared in accordance with the principles of the present invention according to a number of known manufacturing methods. Generally, such methods involve the preparation of a binder or a multiple binder system, mixing of the additional ingredients, dispersing of the pigments, and adjusting the density and viscosity to desired levels. A variety of additives and diluents which are well known in the art can be mixed with the binders of the present invention to achieve certain properties in the paint or the coating. The additives may include, but are not limited to, surfactants, defoamers, rheology modifiers, coalescents, biocides, mildewcides, surfactants, and other additives well known in the art.
In one embodiment, a paint in accordance with the principles of the present invention is manufactured to a VOC (Volatile Organic Compounds) of 150 gr/L, including a 37% solid by volume, a 51% solid by weight, a 34 PVC, and a 1.5 pigment/binder ratio.
The PVC of paint in accordance with the principles of a preferred form of the present invention may vary between 4-55 by weight. In one embodiment of the present invention the paint is a “semi-gloss paint”, which has a relatively low PVC. In another embodiment of the present invention, the paint is a “satin paint”, which has a relatively high PVC. In another embodiment of the present invention, the paint is a “flat paint”, which has a relatively high PVC compared to satin paint.
Table 1 lists the general ranges of the main ingredients of a paint in accordance with the principles of a preferred embodiment. The total amount of polymer (i.e., binder) is preferably between about 30-60 gallons per 100 gallons. In one embodiment, the ratio of the first binder to the second binder is about 80:20. The first binder is, in one embodiment, a self-crosslinking polymer. The total amount of pigment, excluding the TiO2, is preferably between about 15 and about 150 pounds per 100 gallons. The TiO2 content is preferably between 0 pounds per gallon and about 360 pounds per 100 gallons. The preservatives comprise between about 5 and about 8 pounds per 100 gallons. Additional additives comprise approximately 50 and approximately 200 pounds per 100 gallons. Water comprises between about 50 and about 200 pounds per 100 gallons. The paint further includes additional solvent, aside from the water content of between about 30 and about 45 pounds per 100 gallons. In one embodiment, the nanoparticle metal oxide pigment particles have an average particle size of less than about 100 nanometers. In a further embodiment, the nanoparticle metal oxide pigment particles have an average particle size of between about 30 nanometers and about 65 nanometers.







TABLE 1







Ingredients Range










Pounds/100 Gallons












Category
Minimum
Maximum















Additive
50.00
200.00



Polymer (resin)
450.00
635.00



Pigment
15.00
150.0



Titanium Dioxide
0.00
360.00



Preservative
5.0
8.0



Water
50.00
200.00



Solvent
0.00
45.00



Total
600
1598



Volume % Solids
25
40



Weight % Solids
30
55



PVC
4
55










The preferred formulation process consists of two conventional steps: the grind and the letdown. During the grind, the solvent (water), dispersant, defoamer, zinc oxide, ethylene glycol, amino alcohol, nepheline syenite, attapulgite clay are mixed together. During the letdown, the binder, the mildewcide, the rheology modifier, and the biocide, are added to the grind product.
The following non-limiting examples illustrate main components of the paint formulations and the paint formulations themselves. Table 2 provides the material ranges for the components of the paint formulations of Examples 1-4.







TABLE 2







Raw Material Ranges











Range in



Raw Material
lbs/100 gal







Water
 70-220



Copolymer Dispersant
10-20



Nano Particle Inorganic Oxide
 4-20



Zinc Oxide
0-7



Phosphated Co-Ester Surfactant
3-6



Mineral Oil Defoamer
4-8



Nepheline Syenite
 10-305



Glycol
 0-35



Rheology Modifier
15-30



100% Acrylic Primer Binder
340-430



100% Acrylic Topcoat Binder
 70-100



Styrene Acrylic Topcoat Binder
 0-180



Coalescent
 0-15



In-can Biocide
0.5-2  



Mildewcide
6-8



Non-ionic Rheology Modifier
 7-25



Amino Alcohol
0-1



Titanium Dioxide
 0-350



Bentonite
0-6



Fluoro Surfactant
  0-0.4



Opaque Polymer
 0-110



Attapulgite Clay
0-8



Non-ionic Surfactant
0-5



Calcined Diatomaceous
 0-45










Example 1
Semi-Gloss Finish
Example 1 was formulated using the basic components of Table 2, with the following specific components:











TABLE 3







Description
Amount
Weight %
















Grind











Water
73.92
6.98



Copolymer Dispersant
15.02
1.42



Mineral Oil Defoamer
2.00
0.19



Zinc Oxide
5.00
0.47



Nano Particle Metal Oxide
3.00
0.28



Ethylene Glycol
32.00
3.02



Amino Alcohol
0.50
0.05



Non-ionic Surfactant
4.00
0.38



Nepheline Syenite
10.00
0.94



Attapulgite Clay
5.00
0.47







Letdown











100% Acrylic Primer Vehicle
410.65
38.77



100% Acrylic Topcoat Vehicle
86.44
8.16



Mineral Oil Defoamer
3.00
0.28



TiO2 Slurry
297.00
28.04



Coalescent
8.00
0.76



Associative RM
28.00
2.64



Non-ionic HEUR RM
8.00
0.76



Opaque Polymer
58.80
5.55



Phosphated Co-ester Surfactant
1.00
0.09



Mildewcide
6.94
0.65



In-can Biocide
1.00
0.09










Example 2
Satin Finish
Example 2 was formulated using the basic components of Table 2, with the following specific components:










TABLE 4







Amount
Weight %
















Grind











Water
45.35
4.06



Copolymer Dispersant
15.02
1.35



Mineral Oil Defoamer
3.00
0.27



Nano Particle Metal Oxide
15.00
1.34



Ethylene Glycol
37.00
3.32



Amino Alcohol
0.50
0.04



Non-ionic Surfactant
2.00
0.18



Nepheline Syenite
105.02
9.41



Attapulgite Clay
5.01
0.45







Letdown











100% Acrylic Primer Vehicle
410.60
36.82



100% Acrylic Topcoat Vehicle
86.43
7.75



TiO2 Slurry
294.32
26.39



Coalescent
8.00
0.72



Phosphated Co-ester Surfactant
1.00
0.09



Associative RM
25.00
2.24



Non-ionic HEUR RM
4.00
0.36



Opaque Polymer
50.05
4.49



Mildewcide
6.94
0.62



In-can Biocide
1.00
0.09










Example 3
Flat Finish
Example 3 was formulated using the basic components of Table 2, with the following specific components:










TABLE 5







Amount
Weight %
















Grind











Water
25.27
2.18



Ethylene Glycol
22.55
1.95



Non-ionic Surfactant
2.00
0.17



Copolymer Dispersant
15.3
1.32



Zinc Oxide
4.92
0.42



Nano Particle Metal Oxide
4.92
0.43



Amino Alcohol
0.98
0.09



Mineral Oil Defoamer
1.97
0.17



Nepheline Syenite
94.7
8.18



Attapulgite Clay
7.92
0.68



Phosphated Co-ester Surfactant
3.87
0.33







Letdown











TiO2 Slurry
350.02
30.26



Water
82.22
7.1



Calcined Diatomaceous Earth
44.28
3.82



100% Acrylic Primer Vehicle
285.04
24.64



100% Acrylic Topcoat Vehicle
60.02
5.19



Opaque
105.79
9.15



Coalescent
7.87
0.68



Associative RM
18.81
1.63



Mildewcide
6.82
0.59



Mineral Oil Defoamer
3.94
0.34



Non-ionic HEUR RM
6.43
0.56



In-can Biocide
0.96
0.08










Example 4
Flat Finish
Example 4 was formulated using the basic components of Table 2, with the following specific components:










TABLE 6







Amount
Weight %
















Grind











Water
197
21.15



Ethylene Glycol
30
3.22



Non-ionic Surfactant
1.00
0.85



Copolymer Dispersant
8.0
0.86



Nano Particle Metal Oxide
8.0
0.86



Mineral Oil Defoamer
6.0
0.64



Nepheline Syenite
90.0
9.64



Bentonite
6.0
0.64







Letdown











Opaque
4.0
.43



100% Acrylic Primer Vehicle
366.0
39.3



100% Acrylic Topcoat Vehicle
77.0
8.27



2nd Acrylic Topcoat Vehicle
82.0
8.8



Coalescent
5.0
0.54



Associative RM
18.0
1.9



Mildewcide
6.92
0.74



Non-ionic HEUR RM
25
2.68



In-can Biocide
1.0
0.1










Adhesion Tests
Various adhesion tests were performed to determine the adhesion properties of a paint in accordance with the principles of the present invention on different substances. The results of the tests compare a paint of the present invention to a typical, commercially-available paint and primer system sold for exterior use, and these tests are presented in Table 7.







TABLE 7







Adhesion Test Results Rated by ASTM D3359













Paint Formulation
Acrylic Exterior
Acrylic Exterior




of the present
Primer*
Topcoat*


Adhesion Test
Test Condition
invention
(Control)
(Control)





Alkyd






green
overnight, dry/wet
5B/4B
5B/4B
5B/5B


gray
overnight, dry/wet
5B/5B
5B/5B
5B/5B


Chalk


blue latex panel
overnight, dry/wet
5B/5B
5B/4B
5B/5B


Wood


Cedar
overnight, dry/wet
4B/5B
3B/3B
4B/5B


Oak
overnight, dry/wet
5B/5B
5B/4B
5B/5B


Redwood
overnight, dry/wet
5B/5B
5B/4B
5B/5B


PT green
overnight, dry/wet
5B/5B
5B/5B
5B/5B


Vinyl Siding


new vinyl
overnight, dry/wet
5B/5B
5B/5B
5B/5B


weathered vinyl
overnight, dry/wet
5B/5B
5B/5B
5B/5B


Metals


galvanized steel
overnight, dry/wet
4B/5B
3B/3B
0B/0B



3 day, dry/wet
5B/3B
4B/4B
0B/0B


aluminum roll
overnight, dry/wet
2B/3B
3B/3B
0B/0B



3 day, dry/wet
4B/5B
4B/4B
0B/0B


Miscellaneous


glossy black tile
overnight, dry/wet
5B/3B
2B/0B
0B/0B



3 day, dry/wet
5B/5B
5B/2B
0B/0B


clay tile
overnight, dry/wet
5B/3B
1B/0B
1B/0B



3 day, dry/wet
5B/5B
5B/5B
3B/0B


bull nose brick
overnight, dry/wet
5B/0B
4B/0B
4B/0B



3 day, dry/wet
5B/0B
5B/0B
2B/0B





*The control Acrylic Exterior Primer and Control Acrylic Exterior Topcoat tested were at least comparable to those readily available on the commercial market.






In addition, a battery of tests were performed to evaluate the overall performance of a paint in accordance with the principles of the present invention at various sheens as compared to paints currently available in the marketplace. As shown in the results in Tables 8 and 9, the paint prepared in accordance with the principles of the present invention outperformed all of the other paints in the respective category.







TABLE 8







Flat Sheen Benchmarking Composite Scores













Super
Commercial





Exterior
Acrylic
Possible



Test
Flat
Flat**
Score
















Freeze-Thaw
1
0
2



Heat Stability
1.5
3
3



Applied Holding
7.5
5
10



Leveling
5
0
5



Touch-up
7.5
10
10



Drying Time
2
2
2



Sag Resistance
3
3
3



Roller Foam
3
3
3



Roller Spatter
1
0.5
1



3 mil Contrast
20
6
20



Ratio



Dry Adhesion
12
7.5
15



Blistering
9
9
9



Resistance



Wet Adhesion
15
15
15



Water Spotting
2
2
2



Total Score
89.5
66
100







**The Commercial Acrylic Flat paint tested was at least comparable to those readily available on the commercial market.






As seen in Table 9, the satin sheen of the present invention exhibits improved leveling, roller foam, contrast, and dry adhesion.







TABLE 9







Satin Sheen Benchmarking Composite Scores













Commercial





Super
Acrylic
Commercial



Exterior
Exterior
Silicone Acrylic
Possible


Test
Satin
Satin***
Exterior Satin***
Score














Freeze-Thaw
2
1
2
2


Heat Stability
3
3
3
3


Applied Holding
10
5
10
10


Leveling
5
2.5
0
5


Touch-up
7.5
4
7.5
10


Drying Time
2
2
2
2


Sag Resistance
3
3
3
3


Roller Foam
3
3
1.5
3


Roller Spatter
1
1
1
1


3 mil Contrast
20
20
14
20


Ratio


Dry Adhesion
12
0
12
15


Blistering
15
7
15
9


Resistance


Wet Adhesion
9
15
9
15


Water Spotting
2
2
2
2


Total Score
94.5
68.5
82
100





***The Commercial Acrylic Satin Exterior and Commercial Silicone Acrylic Exterior Satin tested were at least comparable to those readily available on the commercial market.






As illustrated in FIGS. 1, 2, 3, 4, and 5, paint prepared in accordance with the principles of the present invention exhibits improvements in adhesion, tannin blocking, stain removal, hiding power, and corrosion resistance. FIG. 1 depicts a multi-axis property graph of the test results of paint of the present invention having a satin sheen and white base, as compared to commercially-available, exterior satin in a white base. Adhesion, yellowing, stain removal, hiding power, scrub resistance, corrosion, and tannin blocking were measured. FIG. 2 depicts a multi-axis property graph of the test results of flat white base paint in accordance with the principles of the present invention, as compared to a commercially available exterior flat paint in a white base. FIG. 3 illustrates a multi-axis property graph of the test results for semi-gloss white base paint of the present invention versus a commercially available exterior semi-gloss paint in a white base. All properties were improved in formulations in accordance with the principles of the present invention with the exception of scrub resistance and yellowing, which showed a reduction. FIG. 4 illustrates a multi-axis property graph for a flat white base paint of the present invention versus a second commercially-available, exterior flat paint in a white base. All properties were improved in formulations in accordance with the principles of the present invention. FIG. 5 illustrates a multi-axis property graph for a satin white base paint of the present invention verses a second commercially-available, exterior satin paint in a white base. All properties were improved in formulations in accordance with the principles of the present invention.
While several embodiments have been shown and described in this application, it is understood that changes and modifications can be made to the invention without departing from the invention's broader aspects.

## Claims

1. A process for producing a paint composition comprising the steps of:
dispersing a titanium dioxide pigment particles in a solvent to form a dispersion;
mixing the dispersion with grind additives and metal oxide nanoparticles having an average particle size of less than 100 nanometers;
adding a first acrylic primer binder consisting of a 100% acrylic resin and a second acrylic topcoat binder consisting of a 100% acrylic resin to the dispersion; and
adding letdown additives to the dispersion, wherein the resulting composition includes a PVC of about 4 to about 55 and a percentage of solid by weight of between about 30 and about 55;
wherein the ratio of the first acrylic primer binder to the second acrylic topcoat binder is about 80:20.

2. The process of claim 1, wherein the metal oxide nanoparticles comprise zinc oxide.

3. The process of claim 1, wherein the metal oxide nanoparticles comprise particles having an average particle size of between about 30 nanometers and about 65 nanometers.

4. The process of claim 1, wherein the first acrylic primer binder comprises a self-crosslinking polymer.

5. The process of claim 1, wherein the weight ratio of metal oxide nanoparticles to 100% acrylic resin in the paint is in the range from 0.0075:1 to 0.049:1.

6. A process for producing a paint composition comprising the steps of:
dispersing a titanium dioxide pigment particles in a solvent to form a dispersion;
mixing the dispersion with grind additives and metal oxide nanoparticles having an average particle size of less than 100 nanometers;
adding a first acrylic primer binder consisting of a 100% acrylic resin and a second acrylic topcoat binder consisting of a 100% acrylic resin to the dispersion; and
adding letdown additives to the dispersion, wherein the resulting composition includes a PVC of about 4 to about 55 and a percentage of solid by weight of between about 30 and about 55;
wherein the weight ratio of the first acrylic primer binder to the second acrylic topcoat binder is in the range from 3.4:1 to 6.1:1.