Search Images Maps Play Gmail Drive Calendar Translate More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberWO1997012945 A1
Publication typeApplication
Application numberPCT/US1996/015940
Publication date10 Apr 1997
Filing date4 Oct 1996
Priority date6 Oct 1995
Publication numberPCT/1996/15940, PCT/US/1996/015940, PCT/US/1996/15940, PCT/US/96/015940, PCT/US/96/15940, PCT/US1996/015940, PCT/US1996/15940, PCT/US1996015940, PCT/US199615940, PCT/US96/015940, PCT/US96/15940, PCT/US96015940, PCT/US9615940, WO 1997/012945 A1, WO 1997012945 A1, WO 1997012945A1, WO 9712945 A1, WO 9712945A1, WO-A1-1997012945, WO-A1-9712945, WO1997/012945A1, WO1997012945 A1, WO1997012945A1, WO9712945 A1, WO9712945A1
InventorsDavid E. Culp, Rudiger Laufhutte, Michael A. Lucarelli, Bob Tse-Weng Lin, Gregory W. Leman, Helmut T. Lehmann
ApplicantCabot Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: Patentscope, Espacenet
Aqueous thixotropes for waterborne systems
WO 1997012945 A1
Abstract
Aqueous thixotropes for waterborne systems are disclosed including an aqueous dispersion of fumed silica and a waterborne resin. The waterborne resin is selected from the group consisting of alkyd, acrylic, polyester, polyether, silicate, urethane, epoxy, formaldehyde, vinyl, and mixtures thereof. The fumed silica has a surface area between about 85 m2/g and about 410 m2/g, and is present in the system in an amount between about 0.5 and about 10.0 % by weight, of total resin solids.
Claims  (OCR text may contain errors)
1. A waterborne system, comprising: an aqueous dispersion of fumed silica; and a waterborne resin; wherein said fumed silica has a surface area between about 85 m2/g and about 410 m2/g.
2. The waterborne system of claim 1 , wherein said fumed silica has a surface area between about 175 m2/g and about 225 πr/g.
3. The waterborne system of claim 2, wherein said fumed silica has a surface area of about 200 m2/g.
4. The waterborne system of claim 1, wherein said fumed silica has an impurity level of less than 1 % .
5. The waterborne system of claim 1 , wherein said system comprises between about 0.5 and about 10.0% fumed silica, by weight, of total resin solids.
6. The waterborne system of claim 5, wherein said system comprises between about 0.5 and about 5.0% fumed silica, by weight, of total resin solids.
7. The waterborne system of claim 6, wherein said system comprises about 2.0% fumed silica, by weight, of total resin solids.
8. The waterborne system of claim 1, wherein said aqueous dispersion of fumed silica has between 10% and 45 %, by weight, silica solids.
9. The waterborne system of claim 8, wherein said aqueous dispersion of fumed silica has between 15 % and 30%, by weight, silica solids.
10. The waterborne system of claim 9, wherein said aqueous dispersion of fumed silica has 20% , by weight, silica solids.
11. The waterborne system of claim 1 , wherein said aqueous dispersion of fumed silica has a pH between about 5.0 and about 10.5.
12. The waterborne system of claim 11 , wherein said aqueous dispersion of fumed silica has a pH between about 7.0 and about 9.5.
13. The waterborne system of claim 1, further comprising at least one additive selected from the group consisting of surfactants, coalescing solvents, pigments, defoamers, antiskinning agents, drying agents, wetting agents, thickening agents, dispersing agents, biocides, and corrosion inhibitors.
14. The waterborne system of claim 1, wherein said waterborne resin is selected from the group consisting of alkyd, acrylic, polyester, polyether, silicate, urethane, epoxy, formaldehyde, vinyl, and mixtures thereof.
Description  (OCR text may contain errors)

TITLE

AQUEOUS THIXOTROPES FOR WATERBORNE SYSTEMS

BACKGROUND OF THE INVENTION

1. Field of Invention:

The present invention relates to aqueous thixotropes for waterborne systems and, more particularly, to aqueous dispersions of fumed silica for use as effective thixotropes and rheology control agents in waterborne systems.

2. Description of the Related Art:

Both hydrophilic and hydrophobic fumed silicas are widely used in the coating industry to improve rheology, for flow control and storage stability, as well as serve as an anti-settling agent for pigments and fillers. The production of hydrophilic fumed silica is a well known process. Grades vary in particle and aggregate size. Hydrophobic silica can be produced by treating a fumed silica with a suitable agent which will vary depending on the desired degree of hydrophobicity and other characteristics. Such treating agents include, for example, polydimethylsiloxane oils of various molecular weights, dimethyldichlorosilane, trimethoxyoctylsilane, disilazanes, such as hexamethyldisilazane (HMDZ),and mixtures thereof.

In aqueous systems, which include both emulsions and water reducible vehicles, untreated (hydrophilic) silicas are typically not effective because of the large concentrations of silica that are necessary to realize the desired thickening. However, methods exist for increasing the thickening capability of a given concentration of silica by using certain substances as additives to modify the nature of the system. For example, in systems that are not readily responsive to fumed silica because of inherent chemical properties, the correct additive can often facilitate efficient viscosity and thixotropic control. For example, in highly hydrogen-bonding liquids, the additives that are typically most useful in improving the thickening and thixotropic efficiency of fumed silica are cationic surfactants. The surfactants modify and partially impede the interaction between fumed silica and the solvent, thereby allowing the fumed silica network structure to develop, thus resulting in improved viscosity, thixotropy, and suspending properties. In non- hydrogen-bonding liquids, the additives which prove most useful are short chain molecules with more than one functional group capable of hydrogen bonding, such as glycols. These molecules act as bridging compounds between the surface hydroxyls of fumed silica aggregates, which form chains consisting of alternating silica aggregates and organic molecules. Such systems require the separate addition of certain additives to untreated silica dispersions.

As environmental awareness increases, manufacturers face increased pressure to replace conventional solvent based systems. As a result, aqueous systems are increasingly used in many applications such as automotive and industrial coatings, paints, inks, adhesives, and the like. While hydrophilic and hydrophobic silicas have both been used in solvent-based coating formulations on a commercial scale, their use in aqueous formulations have been plagued with disadvantages. For example, in aqueous systems, either the silica additive must be increased to unacceptable levels or the formulation does not attain the desired level of performance. A demand, therefore, exists for aqueous systems which perform comparably to solvent based systems and, accordingly, for improved additives or methods to accomplish such results.

It is therefore an object of the present invention to provide a versatile and efficient rheological additive for waterborne systems, such as in coatings and other industrial applications.

A further object is to provide an additive that fosters stability in aqueous compositions. A still further object is to provide a thixotrope which alleviates many of the waterborne coating rheology control formulating difficulties that exist with other inorganic and organic materials .

SUMMARY OF THE INVENTION

Accordingly, the present invention is directed to an aqueous dispersion of fumed silica that provides enhanced rheology control and thixotropy to waterborne systems. The fumed silica dispersion is uniformly dispersed in the waterborne system such that an amount ranging between 0.5 % and 10.0 % , by weight, of silica is present in the final composition. The waterborne system, therefore, includes an aqueous dispersion of fumed silica, and a waterborne resin. The resin is selected from the group consisting of alkyd, acrylic, polyester, polyether, silicate, urethane, epoxy, formaldehyde, vinyl, and mixtures thereof. The fumed silica has a surface area between about 85 m2/g and about 410 m2/g. BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the rheological performance of an epoxy resin system incorporating the present fumed silica dispersion;

FIG. 2 is a graph of the rheological performance of an bisphenol-A epoxy resin system incorporating the present fumed silica dispersion;

FIG. 3 is a graph of the rheological performance of an epichlorohydrin and bisphenol-A resin system incoφorating the present fumed silica dispersion;

FIG. 4 is a graph of the rheological performance of a urethane modified epoxy resin system incoφorating the present fumed silica dispersion; and FIG. 5 is a graph of the rheoiogical performance of an acrylic resin system incoφorating the present fumed silica dispersion; and

FIG. 6 is a graph of the response of the present fumed silica dispersion in a typical water reducing alkyd coating formulation.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to an aqueous dispersion of hydrophilic fumed silica which provides enhanced rheology control and thixotropy to aqueous or waterborne systems. The present aqueous dispersion of fumed silica is effective in alkyd, acrylic, polyester, polyether, silicate, urethane, epoxy, formaldehyde, vinyl, and mixtures or modifications thereof as vehicle systems. It has been found that unlike other organic and inorganic materials used as thixotropes in waterborne systems such as coatings, the present aqueous dispersion of fumed silica will not typically react with additives in the formulation to produce unexpected side effects after product manufacture.

Fumed silicas useful in this invention are generally characterized by a chain-like structure having high surface area per unit weight. The production of fumed silica is a well-documented process which involves the hydrolysis of silicon tetrachloride vapor in a flame of hydrogen and oxygen. Molten particles of roughly spherical shapes are formed in the combustion process, the diameters of which are varied through process parameters. These molten spheres of fumed silica, typically referred to as primary particles, fuse with one another by undergoing collisions at their contact points to form branched, three dimensional chain-like aggregates. The force necessary to break aggregates is considerable and often considered irreversible because of the fusion. During cooling and collecting, the aggregates undergo further collision that may result in some mechanical entanglement to form agglomerates. Compared to the aggregates where the primary particles are fused together, agglomerates are thought to be loosely held together by Van der Waals forces and can be reversed, i.e. de-agglomerated, by proper dispersion in suitable media.

The size of the primary spherical particles that comprise the fumed silica aggregates determine the surface area. The surface area of the fumed silica, as measured by the nitrogen adsoφtion method of S. Brunauer, P. H. Emmet, and I. Teller, J. Am. Chemical Society, Volume 60, Page 309 (1938) and commonly referred to as BET, typically ranges from about 85 m2/g to about 410 πr/g. In the present invention, the fumed silica is preferably in a range from about 175 m2/g to about 225 m2/g, and are of a high purity. High purity means that the total impurity content is typically less than 1 % and preferably less than 0.01 % (i.e., 100 ppm). Although many commercially available fumed silicas are suitable, CAB-O-SIL® fumed silica, available from the Cab-O-Sil Division of Cabot Coφoration, Tuscola, IL, having a surface area of about 200 m2/g is most preferred. Such a silica has been found to be of high quality and is readily dispersable.

The fumed silica of the present invention is uniformly dispersed in a stable aqueous medium (e.g. deionized water) using conventional methods known to those skilled in the art. By uniformly dispersed is meant that the aggregates are isolated and well distributed throughout the medium. By stable is typically meant that the aggregates will not re-agglomerate and settle out (e.g. form a hard, dense sediment). The fumed silica dispersion should have a pH between 5.0 and 10.5 and may be adjusted by the addition of a suitable base such as sodium hydroxide, potassium hydroxide, ammonia and the like. Preferably, the fumed silica dispersion of the present invention has a pH ranging between 7.0 and 9.5. The fumed silica dispersion of the present invention is preferably prepared by the method described by Miller et al., in U.S. Patent No. 5,246,624, the disclosure of which is incoφorated herein in its entirety by reference. Although many commercially available fumed silica dispersions are suitable, CAB-O-SPERSE® aqueous fumed silica dispersions, available from the Cab-O-Sil Division of Cabot Coφoration, Tuscola, IL, are most preferred.

The waterborne systems of the present invention are prepared by combining or mixing the aqueous dispersions of fumed silica directly with a waterborne resin, such as an alkyd, acrylic, polyester, silicate, urethane, epoxy, and the like, or with a formulation containing a waterborne resin under low shear conditions (i.e., to prevent foaming) until a uniform homogeneous composition is obtained. Typically, the fumed silica dispersions range from about 10% to about 45 % solids, by weight; and, preferably, between 15% and 30% solids, by weight. Most preferably, a fumed silica dispersion of about 20 % solids, by weight, has been found to maximize the loading level of silica while maintaining the colloidal stability of the dispersion.

The aqueous dispersions of fumed silica of the present invention are useful in aqueous systems to provide effective rheological control (i.e., viscosity and thixotropy) for example, in industrial and automotive coating, adhesive, paint, and ink applications. It has been found that another advantage of using an aqueous dispersion of fumed silica in waterborne resin systems is to provide rheology and sag control, and anti-settling. It is also believed that a stable matrix is formed in waterborne formulations after the incoφoration of the fumed silica dispersion due to electrostatic interaction. During the high-shear processes usually found in product application, the matrix disintegrates, thereby reducing viscosity and permitting near-Newtonian flow. After application, the inorganic matrix reforms at a predictable rate to provide resistance to sagging and edge-pull during film coalescence and/or cure. This matrix remains unmodified through the many physical film changes during conversion from liquid to solid, thus providing a predictable application consistency.

The aqueous dispersion of fumed silica has been found to be an effective suspension agent in some formulations due to its internally-generated structure. The product forms a matrix capable of stopping or significantly retarding undesirable striation and pigment settling, even in products containing powdered zinc or other unusually heavy pigments. It is noted that the addition of dry hydrophilic fumed silica to waterborne systems has been found to be ineffective as a rheology control agent. In particular, the viscosity of the system will tend to continually increase over time, thereby not achieving stability. In addition, the dry silica is difficult to handle and disperse, and may tend to settle out at higher loading levels.

Other advantages of the present dispersions are that they will not migrate in wet or dry films and are unaffected by heat and atmospheric exposure in the dried/cured film. The dispersion is inherently non-yellowing and will not contribute to color changes or drift in either the wet or dry state. Moreover, the present aqueous dispersions of fumed silica are biologically inactive and is not expected support microbial activity.

The present aqueous dispersions of fumed silica used as aqueous thixotropes in water based systems are responsive to changes in pH, but have been found to be effective in the 7.0 to 9.5 pH range commonly used in products formulated for industrial and commercial use. The present dispersions have also been found to be effective in higher pH ranges, depending specifically upon the individual formulation.

Although the loading level, as a percent of total or resin solids, the precise method of incoφoration, and the stage of manufacture at which this is accomplished, all play a significant role in the final effectiveness of the dispersion, the aqueous dispersion of fumed silica of the present invention has been shown to be effective in many systems used in formulating waterborne products.

The present invention will be further illustrated by the following examples, which are intended to be illustrative in nature and are not to be considered as limiting the scope of the invention.

EXAMPLE I

An aqueous colloidal dispersion of fumed silica, which can be used as an aqueous thixotrope in the present invention, was prepared and evaluated as follows.

Approximately 205.24 grams of deionized water and 0.4 gram of 38% hydrochloric acid were added to a commercial Waring blender. While mixing, 80 grams of CAB-O-SIL® PTG grade fumed silica were added to the blender. When the addition was complete, the mixture was stirred at a high rate for about five minutes. After the stirring was completed, about 108.52 grams of water were added to the mixture followed by about 6.12 grams of a 10% potassium hydroxide solution stabilizer. After the addition of the stabilizer, the mixture was stirred for an additional two minutes. The aqueous fumed silica dispersion prepared had a 20% solids level, a viscosity of about 65 centipoise, and a pH of 9. EXAMPLE II

A scaled-up volume of the dispersion of EXAMPLE I was prepared, using 2-amino-2- methyl-1 -propanol, available as AMP-95™ from Angus Chemical Company, Buffalo Grove, IL, as the base-stabilizer. Approximately 1283.80 grams of water were mixed with 0.251 gram of 38 % hydrochloric acid. About 499.92 grams of CAB-O-SIL® PTG grade fumed silica were then added to the water/acid mixture, and was stirred for about 20 minutes. 678 grams of deionized water was then added to the mixture, followed by 10.54 grams of the AMP-95™ stabilizer. The aqueous fumed silica dispersion prepared had a 20.22% solids level, and a pH of 9.

EXAMPLE III

A waterborne system, including an aqueous fumed silica dispersion (similar to the dispersion prepared in EXAMPLE I) and a waterborne epoxy resin, was prepared and evaluated to determine the effectiveness of the present dispersion as a thixotrope for waterborne systems. The aqueous fumed silica dispersion was mixed with Wateφoxy® 701 Resin epoxy curing agent, available from Henkel Coφoration, Ambler, PA, until a loading level of 2% dry silica on resin solids was achieved. The viscosity (centipoise), shear thinning index (STI), and pH were then measured after sample preparation (0 days), and after periods of 1 and 7 days. The viscosity was measured on a Brookfield viscometer using Nos. 3 or 4 spindle at 6 and 60 RPM's. The experimental results are presented below in Table 1.

TABLE 1

DAYS 0 1 7

VISCOSITY

Sample 1, 6 RPM 1500 1500 1500

Sample 1, 60 RPM 1442 1442 1442

Sample 2, 6 RPM 3300 3900 3800

Sample 2, 60 RPM 1990 2540 2590 STI

Sample 1 1.04 1.04 1.04

Sample 2 1.66 1.53 1.51

pH

Sample 1 11.33 11.33 11.33

Sample 2 11.29 11.41 10.99

FIG. 1 is a graph of the viscosity of a control sample (Sample 1), a waterborne epoxy resin without a rheology control agent, versus the present waterborne system (Sample 2) over time. Both Table 1 and FIG. 1 illustrate that the present waterborne system achieved stable performance after about 1 day and a desired increase in viscosity.

EXAMPLE IV

A waterborne system, including an aqueous fumed silica dispersion (similar to the dispersion prepared in EXAMPLE I) and a waterborne bisphenol-A epoxy resin, was prepared and evaluated to determine the effectiveness of the present dispersion as a thixotrope for waterborne systems. The aqueous fumed silica dispersion was mixed with EPI-REZ® 3510-W-60 nonionic, aqueous dispersion of bisphenol-A epoxy resin, available from Shell Chemical Co. , Houston, TX, until a loading level of 2% dry silica on resin solids was achieved. The viscosity (centipoise), shear thinning index (STI), and pH were then measured after sample preparation (0 days), and after periods of 1 and 7 days. The viscosity was measured on a Brookfield viscometer using Nos. 3 or 4 spindle at 6 and 60 RPM's. The experimental results are presented below in Table 2.

TABLE 2

DAYS 0 1 7

VISCOSITY Sample 1 , 6 RPM 220 220 220

Sample 1, 60 RPM 178 178 178

Sample 2, 6 RPM 520 500 400

Sample 2, 60 RPM 264 270 260

STI

Sample 1 1.24 1.24 1.24

Sample 2 1.97 1.85 1.85

pH

Sample 1 3.41 3.41 3.41

Sample 2 5.70 7.04 7.04

FIG. 2 is a graph of the viscosity of a control sample (Sample 1), a waterborne bisphenol-A epoxy resin without a rheology control agent, versus the present waterborne system

(Sample 2) over time. Both Table 2 and FIG. 2 illustrate that the present waterborne system achieved stable performance, particularly the Sample 2 measured at 60 RPM, and a desired increase in viscosity. The Sample 2 viscosity measured at 6 RPM decreased more rapidly.

EXAMPLE V

A waterborne system, including an aqueous fumed silica dispersion (similar to the dispersion prepared in EXAMPLE I) and a waterborne epichlorohydrin and bisphenol-A epoxy resin, was prepared and evaluated to determine the effectiveness of the present dispersion as a thixotrope for waterborne systems. The aqueous fumed silica dispersion was mixed with EPI- REZ® 3510-WY-55 (55% solids) dispersion of Econ™ 1001F condensation product of epichlorohydrin and bisphenol-A in water, available from Shell Chemical Co. , Houston, TX, until a loading level of 2% dry silica on resin solids was achieved. The viscosity (centipoise), shear thinning index (STI), and pH were then measured after sample preparation (0 days), and after periods of 1 and 7 days. The viscosity was measured on a Brookfield viscometer using Nos. 3 or 4 spindle at 6 and 60 RPM's. The experimental results are presented below in Table 3.

TABLE 3

DAYS 0 1 7

VISCOSITY

Sample 1 , 6 RPM 2700 2700 2700

Sample 1, 60 RPM 1010 1010 1010

Sample 2, 6 RPM 3000 5600 15400

Sample 2, 60 RPM 1130 1950 3700

STI

Sample 1 2.67 2.67 2.67

Sample 2 2.65 2.87 4.16

pH

Sample 1 8.74 8.74 8.74

Sample 2 9.38 9.36 7.40

FIG. 3 is a graph of the viscosity of a control sample (Sample 1), a waterborne epichlorohydrin and bisphenol-A epoxy resin without a rheology control agent, versus the present waterborne system (Sample 2) over time. Both Table 3 and FIG. 3 illustrate that the present waterborne system achieved a desired increase in viscosity while providing semi-stable performance in thixotropy. The Sample 2 viscosity measured 6 RPM increased rapidly. The Sample 2 measured at 60 RPM increased less rapidly and was more stable. EXAMPLE VI

A waterborne system, including an aqueous fumed silica dispersion (similar to the dispersion prepared in EXAMPLE I) and a waterborne urethane modified epoxy resin, was prepared and evaluated to determine the effectiveness of the present dispersion as a thixotrope for waterborne systems. The aqueous fumed silica dispersion was mixed with EPI-REZ® 5520- W-60 nonionic aqueous dispersion of urethane modified epoxy resin, available from Shell Chemical Co., Houston, TX, until a loading level of 2% dry silica on resin solids was achieved. The viscosity (centipoise), shear thinning index (STI), and pH were then measured after sample preparation (0 days), and after periods of 1 and 7 days. The viscosity was measured on a Brookfield viscometer using Nos. 3 or 4 spindle at 6 and 60 RPM's. The experimental results are presented below in Table 4.

TABLE 4

DAYS 0 1 7

VISCOSITY

Sample 1, 6 RPM 5600 5600 5600

Sample 1, 60 RPM 1440 1440 1440

Sample 2, 6 RPM 29450 17200 17900

Sample 2, 60 RPM 3710 2730 2920

STI

Sample 1 3.89 3.89 3.89

Sample 2 7.94 6.30 6.13

pH

Sample 1 3.51 3.51 3.51

Sample 2 7.37 7.53 7.40 FIG. 4 is a graph of the viscosity of a control sample (Sample 1), a waterborne urethane modified epoxy resin without a rheology control agent, versus the present waterborne system (Sample 2) over time. Both Table 4 and FIG. 4 illustrate that the present waterborne system achieved stable performance after about 1 day and a desired increase in viscosity.

EXAMPLE VII

A waterborne system, including an aqueous fumed silica dispersion (similar to the dispersion prepared in EXAMPLE I) and a waterborne acrylic copolymer resin, was prepared and evaluated to determine the effectiveness of the present dispersion as a thixotrope for waterborne systems. The aqueous fumed silica dispersion was mixed with Neocryl® A-639 waterborne acrylic copolymer, available from Zeneca Resins, Wilmington, MA, until a loading level of 2% dry silica on resin solids was achieved. The viscosity (centipoise), shear thinning index (STI), and pH were then measured after sample preparation (0 days), and after periods of 1 and 7 days. The viscosity was measured on a Brookfield viscometer using Nos. 3 or 4 spindle at 6 and 60 RPM's. The experimental results are presented below in Table 5.

TABLE 5

DAYS 0 1 7

VISCOSITY

Sample 1, 6 RPM 480 480 480

Sample 1, 60 RPM 212 212 212

Sample 2, 6 RPM 540 680 580

Sample 2, 60 RPM 254 282 258

STI

Sample 1 2.26 2.26 2.26

Sample 2 2.13 2.41 2.25 pH

Sample 1 6.53 6.53 6.53

Sample 2 6.59 6.49 6.53

FIG. 5 is a graph of the viscosity of a control sample (Sample 1), a waterborne urethane modified epoxy resin without a rheology control agent, versus the present waterborne system (Sample 2) over time. Both Table 5 and FIG. 5 illustrate that the present waterborne system achieved stable performance after about 1 day and desired increase in viscosity.

EXAMPLE VIII

A coating formulation, incoφorating the aqueous fumed silica dispersion of the present invention, a waterborne acrylic resin system, and various additives, was prepared and evaluated to determine the effectiveness of the present dispersion as a thixotrope in coatings. A high gloss waterborne topcoat, based on Neocryl® XK90 acrylic copolymer emulsion, available from Zeneca

Resins, Wilmington, MA, was prepared. The coating formulation, as set forth below in Table

6, was prepared by first mixing the components of Part A in a Waring Blender at high speed for about 5 minutes. The Part B components were then added and dispersed into the Part A mixture in the Waring Blender at high speed for about 5 minutes. The viscosity (mPas), STI, and pH were then measured after periods of 2 days, 25 days, and 60 days. These measurements were taken for a high gloss aqueous top coat formulation without any commercial thickening agent

(Control), and a similar formulation utilizing an aqueous fumed silica dispersion (similar to the dispersion prepared in Example I) as an aqueous thixotrope (Sample). The viscosity of the coatings was measured on a Brookfield Rotary Viscometer RVD-II using spindle Nos. 1 or 2 at speeds of 0.5, 1.0, 2.5, 5.0, and 10.0 RPM. The STI is a ratio of the measured viscosity at 0.5 and 5.0 RPM's. The experimental results are presented below in Table 7.

TABLE 6

FORMULATION CONTROL SAMPLE (WT. %) (WT. %) Part A:

Deionized water 4.96 0.94

Neocryl® XK90 acrylic 23.65 23.56 dispersion

Dehydran™ 1293 defoamer 0.30 0.30 (Henkel)

Disperse™ Ayd W22 0.34 0.34 dispersant (Daniel)

Aqueous Fumed Silica — 5.00 Dispersion (i.e., Example I)

Butyl Glycol-coalescent 1.78 1.77

TiO2 18.78 18.78

Part B:

Butyl Glycol 1.78 1.78

Neocryl®XK90 48.0 47.10

NaNO2, 30% sol'n.-rust 0.41 0.41 inhibitor

100.00 100.00

TABLE 7

DAYS 2 25 60

VISCOSITY (mPas)

Control, 0.5 RPM 100 90 70

1.0 RPM 90 60 70

2.5 RPM 72 58 56

5.0 RPM 66 54 56

10.0 60 52 55 RPM

Sample, 0.5 RPM 2560 1280 1280

1.0 RPM 1720 1040 1080 2.5 RPM 1010 752 784

5.0 RPM 720 620 648

10.0 524 508 536 RPM

STI (0.5/5.0 RPM)

Control 1.52 1.66 1.25

Sample 3.56 2.06 1.98

As illustrated above, the aqueous dispersion of the present invention can be incoφorated not only in resins but also in coating formulations.

EXAMPLE IX

A coating formulation, incoφorating the aqueous fumed silica dispersion of the present invention, a waterborne alkyd resin system, and various additives, was prepared and evaluated to determine the effectiveness of the present dispersion as a thixotrope in coatings. An aqueous industrial maintenance coating based on Resydrol® AY 466 W, 38% , alkyd resin emulsion, available from Hoechst Celanese, Fine Chemicals Division, Charlotte, NC, was prepared. The coating formulation, as set forth below in Table 8, was prepared by mixing the components in a Waring blender at high speed for about 5 minutes. The viscosity (mPas) and STI were then measured after periods of 1, 18 and 60 days. These measurements were taken for an aqueous industrial maintenance coating of formulation with and without a commercial thickening agent (Borchigel™ L75N, 54%), and a similar formulation utilizing an aqueous fumed silica dispersion (similar to the dispersion prepared in Example 1) as an aqueous thixotrope (Sample). The viscosity of the coatings was measured on a Brookfield Rotary Viscometer. The experimental results are presented below in Table 9. FIG. 6 is a graph illustrating the viscosity aging over time, taken from the data in Table 9, and corresponding to a shear rate of 1.4 dynes/sec. At a finess of grind <10 microns (the graph was converted from mPas to centipoise). As illustrated in FIG. 6, the aqueous fumed silica dispersion achieved and maintained a stable workable viscosity for an extended period of time. The Control sample exhibited a high initial increase in viscosity and substantial loss over time. TABLE 8

FORMULATION CONTROL SAMPLE

(WT. %) (WT. %)

Resydrol®AY466 W,38% 70.00 69.02

Aqueous Ammonia, 10% 3.00 2.96

Additol™ VXW 4940 drying 1.30 1.28 agent (Hoechst Celanese)

Titanox™ 2300 (Kronos) 21.24 20.94

Borchigel™ L7SN, 54% 1.86 — thickener

Aqueous Fumed Silica — 4.81 Dispersion (i.e. , Example I)

Additol™ VXW 4973 0.30 0.30 defoamer

Surfynol™ SE-F wetting 0.30 0.30 agent (Air Products)

Additol™ XL 297 0.40 0.39 antiskinning agent

Deionized water 1.60 —

100.00 100.00

TABLE 9

1 18 60

DAYS

VISCOSITY

Control 6.660 4.340 3.472

Control without 0.785 0.588 0.588

Borchigel™ thickener

Sample 1.985 2.940 3.087

STI Control 1.54 1.27 1.66

Control without 3.13 1.81 1.88 thickener

Sample 3.33 4.64 2.63

As illustrated above, the aqueous dispersion of the present invention can be incoφorated not only in resins but also in coating formulations.

Although particular embodiments of the invention have been described in detail for puφoses of illustration, various changes and modifications may be made without departing from the scope and spirit of the invention. Accordingly, die invention is not to be limited except as by the appended claims.

What is claimed is:

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
WO1994018277A1 *8 Feb 199418 Aug 1994Cabot CorporationSurfactant modified silica
EP0399442A2 *21 May 199028 Nov 1990BASF CorporationRheology control additive for waterborne paint compositions
US4455331 *22 Sep 198319 Jun 1984E. I. Du Pont De Nemours And CompanyCoating composition containing a rheology control additive of silica and polyvinyl pyrrolidone
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
WO2003095532A1 *2 May 200320 Nov 2003Basf Coatings AgAqueous dispersion of inorganic nanoparticles, method for the production and use thereof
WO2004085556A1 *22 Mar 20047 Oct 2004Dsm Ip Assets B.V.Aqueous pigmented coating composition with improved open time comprising crosslinkable oligomer(s) and dispersed polymer(s)
WO2005047401A28 Nov 200426 May 2005Basf Coatings AgIntrinsically viscous, aqueous dispersions, method for the production thereof, and use thereof
WO2009115294A117 Mar 200924 Sep 2009Basf Coatings AgCoating composition, method for the production thereof, use thereof and substrates coated therewith
WO2010112106A120 Feb 20107 Oct 2010Basf Coatings AgMoisture-curing coating compositions based on aprotic solvents, comprising binders having alkoxysilane groups, and the use thereof
WO2010139375A18 Mar 20109 Dec 2010Basf Coatings GmbhCoating agents and coatings produced therefrom having high scratch resistance and high blistering resistance
WO2010149236A18 Mar 201029 Dec 2010Basf Coatings GmbhCoating agent and coatings produced therefrom having high scratch resistance while yielding good results in the erichsen depth test and having good stone chipping resistance properties
WO2011029502A13 Aug 201017 Mar 2011Basf Coatings GmbhBinding agent mixture, coating agents containing said binding agent mixture, and coatings produced from said coating agents, said coatings having a high scratch resistance, high weathering stability, and good optical properties
WO2011060858A116 Oct 201026 May 2011Basf Coatings GmbhCoating agents with good storage stability, and coatings produced therefrom with high scratch resistance and simultaneously good weathering resistance
WO2011131461A130 Mar 201127 Oct 2011Basf Coatings GmbhCoating agents having improved runoff tendency
WO2011131463A130 Mar 201127 Oct 2011Basf Coatings GmbhCoating materials with high solids content and good levelling, multi-coat paint systems produced therefrom and use thereof
WO2012065828A128 Oct 201124 May 2012Basf Coatings GmbhPolyurethane coating composition, multilayer surface coatings having a matt surface produced therefrom and processes for producing the multilayer surface coatings
WO2012065942A114 Nov 201124 May 2012Basf Coatings GmbhCoating composition having a high solids content and good levelling and also multilayer surface coatings produced therefrom and their use
WO2012098014A14 Jan 201226 Jul 2012Basf Coatings GmbhAqueous polyurethane coating material and coatings produced therefrom and having high scratch resistance and good chemicals resistance
WO2012113829A122 Feb 201230 Aug 2012Basf SeSulfonium sulfates, their preparation and use
WO2012123161A130 Jan 201220 Sep 2012Basf Coatings GmbhPolyurethane coating material composition, multistage coating methods using these coating material compositions, and also the use of the coating material composition as clearcoat material and pigmented coating material, and application of the coating method for automotive refinish and/or for the coating of plastics substrates and/or of utility vehicles
WO2012123198A110 Feb 201220 Sep 2012Basf Coatings GmbhPolyurethane coating agent composition, multistage coating method using said coating agent compositions, and use of the coating agent compositions as clear coating or pigmented coating material and use of the coating method for automotive repair painting and/or for coating plastic substrates and/or commercial vehicles
WO2012126796A115 Mar 201227 Sep 2012Basf Coatings GmbhZinc-imidazole-carboxylate-complex-catalysed coating agent composition
WO2012140131A112 Apr 201218 Oct 2012Basf Coatings GmbhSolvent-borne clearcoat coating composition, method for producing it and use thereof
WO2012168014A17 May 201213 Dec 2012Basf Coatings GmbhCoating agent compositions, coatings made therefrom and exhibiting high scratch resistance and good polishability, and use thereof
WO2012168079A123 May 201213 Dec 2012Basf Coatings GmbhCoating agent compositions, coatings made therefrom and exhibiting high scratch resistance and good polishability, and use thereof
WO2013076208A122 Nov 201230 May 2013Basf Coatings GmbhSolventborne clearcoat coating composition, process for producing it and use thereof
WO2013110712A124 Jan 20131 Aug 2013Basf Coatings GmbhZinc (1-methylimidazole)bis(2-ethylhexanoate) complex catalyzed coating material composition
WO2013156509A217 Apr 201324 Oct 2013Basf SeSulfonium compounds, their preparation and use
WO2014016019A129 May 201330 Jan 2014Basf Coatings GmbhPolyurethane coating agent compositions, multi-stage coating methods
WO2014016026A14 Jun 201330 Jan 2014Basf Coatings GmbhPolyurethane coating agent composition and use thereof, multi-stage coating methods
WO2014106552A129 Nov 201310 Jul 2014Basf Coatings GmbhOne -component, curable coating composition, processes for making and using them, and coatings and articles prepared with them
WO2015116351A17 Jan 20156 Aug 2015Basf Coatings GmbhAmphiphilic carbamate-functional copolymers and coatings containing them
WO2015169545A113 Apr 201512 Nov 2015Basf Coatings GmbhMethod using titanium catalyst for producing carbamate-functional materials
WO2015169550A114 Apr 201512 Nov 2015Basf Coatings GmbhMethod using zirconium catalyst for producing carbamate- functional materials
WO2016116259A113 Jan 201628 Jul 2016Smartmaterialprinting B.V.Biocidal treatment of objects and water-containing cleaning and body-care products with polyoxometalate microparticles and/or nanoparticles
WO2016120160A122 Jan 20164 Aug 2016Basf Coatings GmbhCoating agent system on the basis of li/bi catalysts
WO2016138243A1 *25 Feb 20161 Sep 2016Polynt Composites USA Inc.Fillers
WO2016150823A117 Mar 201629 Sep 2016Basf Coatings GmbhMethod using zinc catalyst for producing carbamate-functional materials
WO2016166470A113 Apr 201620 Oct 2016Université De Haute-AlsaceMethod for dual photochemical/thermal crosslinking activatable under uv/visible irradiation, and composition for implementing said method
WO2017076754A127 Oct 201611 May 2017Basf Coatings GmbhBiobased hydroxy-urethanes as reactive diluents
WO2017085268A118 Nov 201626 May 2017Covestro Deutschland AgMulti-layer coating structure having a thermally latent catalyst
WO2017182120A118 Apr 201726 Oct 2017WindplusSonne GmbHGas-permeable devices which absorb voc and/or pollutants and/or are biocidal, and use thereof
WO2017182429A118 Apr 201726 Oct 2017Covestro Deutschland AgThermolatently catalysed two-component system
CN102060970A *27 Oct 201018 May 2011中国科学院长春应用化学研究所Method for preparing waterborne resin, and waterborne coating composition
DE10139262C1 *9 Aug 20012 Jan 2003Basf Coatings AgA rheological adjuvant, useful for coating materials, adhesives, and sealing compositions, contains a urea derivative obtained by reaction of isocyanate with sterically hindered primary and secondary monoamines
DE102007015261A127 Mar 20072 Oct 2008Aacure Aadhesives GmbhReactive mass for substrate application, preferably for the generation of a glop-top, comprises a thermally initiable matrix forming material and an energy absorbing initiator, where the initiator is soluble in the reactive mass
DE102007061854A119 Dec 200725 Jun 2009Basf Coatings AgBeschichtungsmittel mit hoher Kratzbeständigkeit und Witterungsstabilität
DE102007061855A119 Dec 200725 Jun 2009Basf Coatings AgBeschichtungsmittel mit hoher Kratzbeständigkeit und Witterungsstabilität
DE102007061856A119 Dec 200725 Jun 2009Basf Coatings AgBeschichtungsmittel mit hoher Kratzbeständigkeit und Witterungsstabilität
DE102008015104A119 Mar 200824 Sep 2009Basf Coatings AgBeschichtungszusammensetzung, Verfahren zu ihrer Herstellung, ihre Verwendung und mit ihr beschichtete Substrate
DE102008030304A125 Jun 200831 Dec 2009Basf Coatings AgVerwendung teilsilanisierter Verbindungen auf Polyisocyanatbasis als Vernetzungsmittel in Beschichtungszusammensetzungen und Beschichtungszusammensetzung enthaltend die Verbindungen
DE102008060454A15 Dec 200810 Jun 2010Basf Coatings AgBeschichtungsmittel und daraus hergestellte Beschichtungen mit hoher Kratzbeständigkeit und Witterungsstabilität sowie guten optischen Eigenschaften
DE102009016195A13 Apr 20097 Oct 2010Basf Coatings AgFeuchtigkeitshärtende Beschichtungsmittel auf der Basis aprotischer Lösemittel enthaltend Bindemittel mit Alkoxysilangruppen und deren Verwendung
DE102009024103A16 Jun 20099 Dec 2010Basf Coatings GmbhBeschichtungsmittel und daraus hergestellte Beschichtungen mit hoher Kratzfestigkeit und hoher Kocherstabilität
DE102009030481A124 Jun 20095 Jan 2011Basf Coatings GmbhBeschichtungsmittel und daraus hergestellte Beschichtungen mit hoher Kratzfestigkeit bei gleichzeitig guten Ergebnissen in der Prüfung der Erichsentiefung und guten Steinschlagschutzeigenschaften
DE102009041380A112 Sep 200924 Mar 2011Basf Coatings GmbhBindemittelmischung und sie enthaltende Beschichtungsmittel sowie daraus hergestellte Beschichtungen mit hoher Kratzbeständigkeit und Witterungsstabilität sowie guten optischen Eigenschaften
DE102009054071A120 Nov 200926 May 2011Basf Coatings GmbhBeschichtungsmittel mit guter Lagerbeständigkeit und daraus hergestellte Beschichtungen mit hoher Kratzfestigkeit bei gleichzeitig guter Witterungsbeständigkeit
DE102009056187A127 Nov 200915 Jul 2010Basf SePolyester resin obtained by polycondensation of mixture comprising polyol, polycarbonic acid, 2-propylheptanoic acid glycidyl ester and/or 4-methyl-2-propylheptanoic acid glycidyl ester, useful e.g. in coating composition
DE102010015675A121 Apr 201027 Oct 2011Basf Coatings GmbhBeschichtungsmittel mit verbesserter Ablaufneigung
DE102010015683A121 Apr 201027 Oct 2011Basf Coatings GmbhCoating agent based on aprotic solvents, useful e.g. as clear coat for automotive repair lacquering, comprises at least one oligomeric and/or polymeric hydroxyl group-containing compound (A) and at least one compound (B)
DE102014006519A13 May 20145 Nov 2015Smart Material Printing B.V.Verwendung magnetischer und/oder magnetisierbarer, polymerer Mikro- und/oder Nanocomposite zur Herstellung komplexer, magnetischer und/oder magnetisierbarer Formteile mithilfe additiver Fabrikatoren
DE102015000812A121 Jan 201521 Jul 2016Smart Material Printing B.V.Wasserhaltige Reinigungs- und Körperpflegemittel mit biozider Wirkung
DE102015000813A121 Jan 201521 Jul 2016Smart Material Printing B.V.Verfahren zur Vernichtung von Medikamenten und Giftstoffen und ihren Metaboliten mithilfe von Polyoxometallat-Mikro-und/oder -Nanopartikeln
DE102015000814A121 Jan 201521 Jul 2016Smart Material Printing B.V.Biozide Ausrüstung von Gegenständen mit Polyoxometallat-Mikro- und/oder -Nanopartikeln
DE102015013981A129 Oct 20159 Mar 2017Svd-Verpackungen GmbhPapier und/oder papierähnliches Material mit funktionalisierter Kohle, Verfahren zur Herstellung des Papiers und/oder papierähnliches Materials und Verwendung des Papiers und/oder papierähnlichen Materials
EP1608712B122 Mar 200424 Aug 2016DSM IP Assets B.V.Aqueous pigmented coating composition with improved open time comprising crosslinkable oligomer(s) and dispersed polymer(s)
EP1897894A124 May 200212 Mar 2008BASF Coatings AGPowder lacquer suspensions (powder slurries) and powder lacquers, method for their manufacture and their application
EP3115381A110 Jul 201511 Jan 2017Université de Haute AlsacePolymerization system using double click michael addition and photopolymerization
US650909612 Apr 200021 Jan 2003Basf Coatings AcLow-yellowing aqueous clear powder coating dispersions, method of making the dispersions, and process for producing clearcoat finishes with the dispersions
US655561214 Jan 200029 Apr 2003Basf Coatings AgAqueous coating material and modular system for producing same
US65556133 Mar 200029 Apr 2003Basf Coatings AgPolyurethane and its use for producing solvent-free coating substances
US662051130 Jun 200016 Sep 2003Basf Coatings AgAqueous coating material, especially aqueous filler or protective base against stones
US663249530 Mar 200014 Oct 2003Basf Coatings AgPyrimidine-based crosslinking agents
US665291924 Feb 200025 Nov 2003Basf Coatings AgHighly scratch-resistant multilayer coat, method for producing and use of the same
US671355917 Aug 200030 Mar 2004Basf Coatings AgSol-gel coating
US67502861 Feb 200015 Jun 2004Basf Coatings AgPolyurethane and its use in aqueous painting plastic
US677032917 Oct 20023 Aug 2004Basf Coatings AgLow-yellowing aqueous clear powder coating dispersions, method of making the dispersions, and process for producing clearcoat finishes with the dispersions
US677709029 Nov 200017 Aug 2004Basf Coatings AgSubstance mixture which can be cured thermally and by using actinic radiation, and the use thereof
US67977711 Feb 200128 Sep 2004Basf Coatings AgAqueous composition that can be hardened physically, thermally or thermally and with actinic radiation and the derivatives and production thereof
US681549425 Mar 20039 Nov 2004Basf Coatings AgAqueous coating material, especially aqueous filler or protective base against stones
US68220385 Jul 200023 Nov 2004Basf Coatings AcAqueous coating substance, method for its production and its use
US690026031 Aug 200031 May 2005Basf Coatings AgUse of associative thickeners based on polyurethane and/or dipropylene glycol monoalkyl ethers in colored and/or decorative effect multi-layered lacquers
US701904222 Aug 200128 Mar 2006Basf Coatings AgThixotropic agent that can be activated using actinic radiation, a method for its production and the use thereof
US701905225 Oct 199928 Mar 2006Basf Coatings AgLiquid substance mixtures and (co)-polymers, method for their production and use thereof for producing complex reactive mixtures
US706758418 Jul 200327 Jun 2006Basf Coatings AgSolvent-containing coating material and the use thereof
US726192618 Jun 200228 Aug 2007Basf Coatings AgSolventborne coating substance that can be cured physically, thermally or thermally and by using actinic radiation and use thereof
US729737530 Jan 200120 Nov 2007Basf Coatings AgAqueous coating material that can be hardened physically, thermally or thermally and with actinic radiation and the utilization thereof
US74167815 Jul 200326 Aug 2008Basf Coatings AgCoatings, methods for producing the same, and the use thereof
US74887692 May 200310 Feb 2009Basf Coatings AgAqueous dispersion of inorganic nanoparticles, method for the production and use thereof
US756963622 Mar 20044 Aug 2009Dsm Ip Assets B.V.Aqueous pigmented coating composition with improved open time comprising crosslinkable oligomer(s) and dispersed polymer(s)
US78038712 May 200328 Sep 2010Basf Coatings GmbhAqueous dispersion of inorganic nanoparticles, method for the production and use thereof
US78794078 Oct 20051 Feb 2011Basf CorporationExtremely scratch-resistant, highly elastic coating agents based on alkoxysilanes
US791532122 Aug 200129 Mar 2011Basf Coatings AgAqueous dispersion and the use thereof in the production of coating agents, adhesives and sealing agents that can be cured by heat or by actinic radiation
US793574624 May 20023 May 2011Basf Coatings AgPowder coating suspension, process for preparing the same and process for preparing powder coating material
US848653922 Aug 200916 Jul 2013Basf Coatings GmbhCoating compositions and coatings produced from them with high scratch resistance, weathering stability, and good optical properties
US856943819 Dec 200729 Oct 2013Basf Coatings GmbhCoating agents having high scratch resistance and weathering stability
US865875225 Jun 200925 Feb 2014Basf Coatings GmbhUse of partially silanized polyisocyanate-based compounds as crosslinking-agents in coating compositions, and coating compositions comprising the compounds
US867958918 Dec 200825 Mar 2014Basf Coatings GmbhCoating agent having high scratch resistance and high weathering resistance
US868609010 Dec 20031 Apr 2014Basf Coatings GmbhUse of urea crystals for non-polymeric coatings
US879075230 Mar 201129 Jul 2014Basf Coatings GmbhCoating materials with high solids content and good levelling, multicoat paint systems produced therefrom and use thereof
US880880518 Dec 200819 Aug 2014Basf Coatings GmbhCoating agent with high scratch resistance and weathering resistance
US886585120 Feb 201021 Oct 2014Basf Coatings GmbhMoisture-curing coating compositions comprising aprotic solvents and binders having alkoxysilane groups and method of forming a multicoat finish therewith
US90178188 Mar 201028 Apr 2015Basf Coatings GmbhCoating compositions and coatings produced from them and featuring high scratch resistance in association with good results in the Erichsen cupping test and good antistonechip properties
US908000214 Sep 200714 Jul 2015Basf Coatings GmbhCoating composition comprising calcium hydrogen-phosphate, processes for preparing it, its use and substrates coated with it
US909073218 Dec 200828 Jul 2015Basf Coatings GmbhCoating composition having a high scratch resistance and weathering stability
US913328326 Jun 201215 Sep 2015General Electric CompanyDual cure compositions, methods of curing thereof and articles therefrom
US913975130 Jan 201222 Sep 2015Basf Coatings GmbhPolyurethane coating material composition, multistage coating methods using these coating material compositions, and also the use of the coating material composition as clearcoat material and pigmented coating material, and application of the coating method for automotive refinish and/or for the coating of plastics substrates and/or of utility vehicles
US920633015 Mar 20128 Dec 2015Basf Coatings GmbhZinc-imidazole-carboxylate-complex-catalysed coating agent composition
US926699317 Mar 200923 Feb 2016Basf Coatings GmbhCoating composition, method for the production thereof, use thereof, and substrates coated therewith
US92669953 Aug 201023 Feb 2016Basf Coatings GmbhBinding agent mixture, coating agents containing said binding agent mixture, and coatings produced from said coating agents, said coatings having a high scratch resistance, high weathering stability, and good optical properties
US926705422 Nov 201223 Feb 2016Basf Coatings GmbhSolvent-containing clearcoat coating composition, process for preparation thereof and use thereof
US932825714 Nov 20113 May 2016Basf Coatings GmbhCoating composition having a high solids content and good levelling and also multilayer surface coatings produced therefrom and their use
US934063831 Jan 201217 May 2016Basf Coatings GmbhPolyurethane coating material composition, multistage coating methods using these coating material compositions, and also the use of the coating material composition as clearcoat material and pigmented coating material, and application of the coating method for automotive refinish and/or for the coating of plastics substrates and/or of utility vehicles
US934070310 Feb 201217 May 2016Basf Coatings GmbhPolyurethane coating agent composition, multistage coating method using said coating agent compositions, and use of the coating agent compositions as clear coating or pigmented coating material, and use of the coating method for automotive repair painting and/or for coating plastics substrates and/or of commercial vehicles
US935328719 Dec 200731 May 2016Basf Coatings GmbhCoating agents having high scratch resistance and weathering stability
US937146923 May 201221 Jun 2016Basf Coatings GmbhCoating agent compositions, coatings made therefrom and exhibiting high scratch resistance and good polishability, and use thereof
US937658616 Oct 201028 Jun 2016Basf Coatings GmbhCoating agents with good storage stability, and coatings produced therefrom with high scratch resistance and simultaneously good weathering resistance
US940401130 Mar 20112 Aug 2016Basf Coatings GmbhCoating agents having improved runoff tendency
US954628528 Oct 201117 Jan 2017Basf Coatings GmbhPolyurethane coating composition, multilayer surface coatings having a matt surface produced therefrom and processes for producing the multilayer surface coatings
US957408916 Aug 201321 Feb 2017Basf Coatings GmbhFluorine-containing nonaqueous coating material composition, coating methods, and the use of the coating material composition
US963104817 Apr 201325 Apr 2017Basf SeSulfonium compounds, their preparation and use
US96311124 Jun 201325 Apr 2017Basf Coatings GmbhPolyurethane coating material composition, multi-stage coating methods, and also the use of the coating material composition
US964411129 May 20139 May 2017Basf Coatings GmbhPolyurethane coating material composition, multi-stage coating methods
US968312529 Nov 201320 Jun 2017Basf Coatings GmbhOne-component, curable coating compositions, processes for making and using them, and coatings and articles prepared with them
US97771904 Jan 20123 Oct 2017Basf Coatings GmbhAqueous polyurethane coating material and coatings produced therefrom and having high scratch resistance and good chemicals resistance
US20090286888 *27 Jul 200919 Nov 2009Cabot CorporationMethod of preparing an aggregate metal oxide particle dispersion having a desired aggregate particle diameter
Classifications
International ClassificationC09D5/04
Cooperative ClassificationB65H2405/422, C09D5/04
European ClassificationC09D5/04
Legal Events
DateCodeEventDescription
10 Apr 1997AKDesignated states
Kind code of ref document: A1
Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN AM AZ BY KG KZ MD RU TJ TM
10 Apr 1997ALDesignated countries for regional patents
Kind code of ref document: A1
Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM
9 May 1997DFPERequest for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
30 Jul 1997121Ep: the epo has been informed by wipo that ep was designated in this application
6 Aug 1998REGReference to national code
Ref country code: DE
Ref legal event code: 8642
4 Sep 1998NENPNon-entry into the national phase in:
Ref country code: JP
Ref document number: 97514463
Format of ref document f/p: F
13 Jan 1999122Ep: pct application non-entry in european phase
6 Apr 1999NENPNon-entry into the national phase in:
Ref country code: CA