阅读说明：本技术 用于油漆制剂的粗颗粒固体非离子合成缔合型增稠剂及其生产方法 (Coarse-particle solid nonionic synthetic associative thickener for paint formulations and method for producing the same ) 是由 K·A·沃伊恩贝里 于 2019-06-13 设计创作，主要内容包括：本公开通常涉及颗粒状产品。所述颗粒状产品包含非离子合成缔合型增稠剂(NSAT)流变改性剂的粗颗粒。所述NSAT流变改性剂选自疏水改性的乙氧基化氨基甲酸酯(HEUR)、疏水改性的聚缩醛聚醚(HMPAPE)和/或其组合。将颗粒状产品掺入到水性油漆配方中。(The present disclosure relates generally to granular products. The granular product comprises coarse particles of a Nonionic Synthetic Associative Thickener (NSAT) rheology modifier. The NSAT rheology modifier is selected from hydrophobically modified ethoxylated urethane (HEUR), hydrophobically modified polyacetal polyether (HMPAPE), and/or combinations thereof. The granular product is incorporated into an aqueous paint formulation.)

1. A granular product comprising a Nonionic Synthetic Associative Thickener (NSAT), wherein the NSAT has an average particle size of from about 0.5mm to about 5.0mm and at least about 10 weight percent of the NSAT is retained on a 1.18mm sieve (No. 16) as measured according to ASTM C136-06 standard test method for sieve analysis of coarse and fine aggregates.

2. The granular product according to claim 1, further comprising a dispersant in an amount of from about 1 to about 15% by weight solids based on the weight of NSAT.

3. The granular product of claim 2, wherein the dispersant comprises silica.

4. The granular product according to any one of claims 1 to 3, wherein at least 20% of the NSAT by weight of solids has an average particle size of 1.18 mm.

5. The granular product according to any one of claims 2 to 4, wherein the amount of dispersant is from about 3 to about 14% by weight solids, based on the weight of NSAT.

6. The granular product according to claim 5 wherein the amount of dispersant is from about 3 to about 10% by weight solids based on the weight of NSAT.

7. The granular product according to claim 6 wherein the amount of dispersant is from about 3 to about 5% by weight solids based on the weight of NSAT.

8. The particulate product according to any one of claims 3 to 7, wherein the silica has an average particle size of greater than 150 nm.

9. The granular product according to claim 8, wherein the silica has an average particle size of from 200nm to 200 μm.

10. The particulate product according to any one of claims 1 to 9, wherein the NSAT is selected from the group consisting of hydrophobically modified polyacetal polyethers (HMPAPEs), hydrophobically modified ethoxylated urethanes (HEURs), hydrophobically modified polyethylene glycols (HMPEGs), and combinations thereof.

11. The particulate product of claim 10, wherein the HMPAPE comprises a polyacetal polyether backbone and a hydrophobic group.

12. The particulate product of claim 11, wherein the hydrophobic group is selected from the group consisting of alkyl, aryl, alkaryl, and cycloaliphatic moieties.

13. The granular product according to claim 12, wherein the hydrophobic group is an alkyl moiety having from about 4 to about 16 carbon atoms.

14. The granular product according to claim 13, wherein the alkyl moiety has from about 4 to about 14 carbon atoms.

15. The granular product according to claim 14, wherein the alkyl moiety has from about 4 to about 12 carbon atoms.

16. The granular product according to any one of claims 1 to 15, further comprising an additional rheology modifier.

17. The granular product of claim 16, wherein the additional rheology modifier comprises a cellulose ether.

18. An aqueous coating composition comprising a film-forming polymer and a particulate product according to any one of claims 1 to 17.

19. The aqueous coating composition of claim 18, wherein the film-forming polymer comprises a latex polymer.

20. The aqueous coating composition of claim 19, wherein the latex polymer is selected from the group consisting of acrylic resins, vinyl acrylic resins, and styrene acrylic resins.

21. The aqueous coating composition of any one of claims 18 to 20, further comprising one or more of a coalescent, a solvent, a wetting agent, a defoamer, a matting agent, a dispersant, a thickener, a biocide, a mildewcide, a pigment, or a surfactant.

22. An aqueous coating composition according to any one of claims 18 to 21, comprising from about 0.1% to about 5% by weight of the granular product of claim 1.

23. The aqueous coating composition of any one of claims 18 to 22, wherein the aqueous composition comprises a paint.

24. A method of producing an aqueous coating composition comprising:

(a) adding a film-forming polymer to the aqueous solution; and

(b) adding the particulate product of any one of claims 1 to 17 to the aqueous solution to form the aqueous coating composition.

25. The method of claim 24, wherein the granular product is added to the aqueous solution prior to adding the film-forming polymer to the aqueous solution.

26. The method of claim 24, wherein the granular product is added to the aqueous solution after the film-forming polymer is added to the aqueous solution.

27. The method of claim 24, wherein the particulate product is added to the aqueous solution at the same time the film-forming polymer is added to the aqueous solution.

28. The method of any one of claims 24 to 27, wherein the film-forming polymer comprises a latex polymer.

29. The method of any one of claims 24 to 28, wherein the aqueous composition comprises a paint.

Technical Field

The presently disclosed and/or claimed methods, procedures, kits, methods, products, results, and/or concepts (hereinafter collectively referred to as "the disclosure") of the present invention generally relate to particulate products for use in aqueous paint formulations and methods of making the same. More particularly, but not by way of limitation, the present disclosure relates to particulate products comprising Nonionic Synthetic Associative Thickeners (NSATs) rheology modifiers. In one non-limiting embodiment, the NSAT rheology modifier is selected from the group consisting of hydrophobically modified ethoxylated urethane (HEUR), hydrophobically modified polyacetal polyether (HMPAPE), hydrophobically modified polyethylene glycol (HMPEG), and combinations thereof. Further, the present disclosure relates to compositions and methods of making aqueous paint formulations comprising a granular product comprising an NSAT rheology modifier having an average particle size of about 0.5 to about 5.0 mm.

Background

Water-soluble polymers (also commonly referred to as "thickeners" or "rheology modifiers") are widely used as additives in many industrial aqueous systems to improve flow characteristics. More specifically, rheology modifiers are designed to impart desirable rheological properties to aqueous systems under specified processing conditions and end use situations.

In recent years, synthetic associative thickeners have gained increasing importance, particularly in controlling the rheology of aqueous coatings and latex paints. Since synthetic associative thickeners are prepared from alkaline chemicals, they can be prepared in consideration of certain characteristics. In other words, the synthetic associative thickener can be tailored to the desired and/or target properties from the outset. Synthetic associative thickeners serve a variety of functions in aqueous systems. For example, in latex paints and aqueous coatings, thickeners provide improved stability and pigment suspension, as well as improved rheology and application properties. In personal care products, thickeners improve the body feel, hand, smoothness and richness of the product, making the product more aesthetically pleasing.

Nonionic Synthetic Associative Thickeners (NSATs) rheology modifiers have been widely used in aqueous paints and coatings because of their ability to provide excellent rheological properties such as, by way of example only, resistance to splashing and sagging, leveling and brushing. NSAT rheology modifiers include, but are not limited to, hydrophobically modified ethoxylated urethane (HEUR), hydrophobically modified polyacetal polyether (HMPAPE), and/or combinations thereof.

Currently, NSAT rheology modifiers are manufactured on production equipment, added to water as a molten solid and dissolved, and then shipped to customers as a polymer in aqueous solution for use in aqueous systems such as aqueous protective coatings. These aqueous solutions are generally highly concentrated, providing as low a viscosity as possible to facilitate pouring, pumping and dosing into paint formulations. The active solids content of these solutions is typically from about 15 to about 25 weight percent.

It is well known that NSAT rheology modifier products delivered in aqueous delivery vehicles are difficult to prepare and suffer from a number of other drawbacks and limitations. The high water content of these products means that customers pay to transport large amounts of water, which wastes fuel and negatively impacts the environment. In addition to excessive shipping costs, these products are often packaged in drums or totes, increasing the packaging cost of the active product. Disposal or recycling of packaging materials is associated with both negative costs and environmental impact. After delivery, the polymer in aqueous solution must be stored in tanks, which imposes ambient temperature storage limitations and requires additional storage space.

NSAT rheology modifier products delivered in solution form can also create problems during the production of aqueous formulations and negatively impact the final product. Aqueous solutions of associative thickeners exhibit high viscosity even at low concentrations due to intermolecular association by their hydrophobic groups. They can also adsorb onto the hydrophobic surfaces of dispersed particles such as latex and pigments. As a result, associative thickeners have a much greater thickening effect than corresponding polymers of the same molecular weight but without hydrophobic groups. In order to make the NSAT rheology modifier product easier to handle in the coating/manufacturing plant, measures must be taken to reduce the viscosity provided to a manageable level.

One known approach to the problem of high viscosity is to dissolve the associative thickener in water and then add the solution to the aqueous formulation. However, this approach limits the amount of polymer that can be dissolved in a certain amount of water without encountering very high viscosities. In addition, water must be added at the appropriate time during the entire manufacturing process, for example as a solvent. This is particularly true in "low" Volatile Organic Compound (VOC) formulations. The use of water to deliver NSAT rheology modifiers limits the product composition and process design flexibility of the manufacturer as the amount of "free" water available is reduced. Furthermore, when final viscosity adjustment is made to achieve the desired paint viscosity, it is undesirable to add water to the paint as this undesirably dilutes the paint ingredients.

Another method commonly used to prevent high viscosity build-up is to add viscosity inhibitors and biocides, such as solvents or surfactants, to reduce the provided viscosity to a manageable level. Unfortunately, these additives not only do not contribute to the properties of the formulated paint, but can also adversely affect key paint properties and contribute to high costs in the final product. Viscosity inhibitors also typically contain VOCs, which are undesirable for health and environmental reasons.

Due to the drawbacks of aqueous delivery, solid formulations of NSAT rheology modifiers have been considered. Whether in aqueous or solid form, it is important to use a NSAT rheology modifier with a particle size small enough (e.g., less than about 1.0mm) to be easily dissolved for controlled processing. See, for example, US 2015/0112000 filed by Prachur bhragova et al, the entire contents of which are incorporated herein by reference, which discloses the use of NSAT rheology modifier pellets wherein less than 5% of such pellets are retained on a 1.18mm sieve (No. 16), or less than 5% of the pellets are retained on a 300 micron sieve (No. 50), or less than about 5% of the pellets are retained on a 150 micron sieve (No. 100). It is well known that small particle NSAT rheology modifiers are readily soluble, resulting in robust incorporation into paint formulations and greater thickening effect.

It has been found that a granular product comprising a Nonionic Synthetic Associative Thickener (NSAT) can be (i) added directly to water, resulting in a non-caking solution in less than 30 minutes of stirring time; and/or (ii) added in powder form at any time during paint production, resulting in complete, rapid, lump-free dissolution and incorporation, said Nonionic Synthetic Associative Thickener (NSAT) having an average particle size of from about 0.5 to about 5.0mm and at least about 10% by weight of said NSAT being retained on a 1.18mm sieve (No. 16) as measured according to ASTM C136-06 standard test method for sieve analysis of coarse and fine aggregates.

Drawings

FIG. 1 is a graph comparing relative torque build-up, depicting a sample of the powder produced in example 4 as comprising the polymer (C) prepared in example 2₁₂HMPAPE), dissolution behavior in aqueous buffer as a function of time.

Fig. 2 is a graph comparing relative torque build-up, depicting dissolution behavior in aqueous buffer over time for the powder sample produced in example 6 as type 3.

FIG. 3 is a graph comparing relative torque build-up, depicting a sample of the powder produced in example 4 as comprising the polymer prepared in example 1 (C)₁₆HMPAPE), dissolution behavior in aqueous buffer as a function of time.

Fig. 4 is a graph comparing relative torque build-up, depicting dissolution behavior in aqueous buffer over time for the powder sample produced in example 5 as type 2.

FIG. 5 is a graph comparing relative torque build-up, depicting a sample of the powder produced in example 4 as comprising the polymer prepared in example 3 (C)₆HMDI-HEUR), dissolution behavior in aqueous buffer over time.

Fig. 6 is a graph comparing relative torque build-up, depicting dissolution behavior in paint as type 3 for the powder samples produced in example 6 at 300rpm and 500rpm as a function of time.

Detailed Description

Before explaining at least one embodiment of the disclosure in detail, it is to be understood that the disclosure is not limited in its application to the details of construction and the arrangement of the components or steps or methods set forth in the following description or illustrated in the drawings. The disclosure is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

Unless otherwise defined herein, technical terms used in connection with the present disclosure shall have the meanings that are commonly understood by those skilled in the art. Furthermore, unless the context requires otherwise, singular terms shall include the plural, and plural terms shall include the singular.

All patents, published patent applications, and non-patent publications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this disclosure pertains. All patents, published patent applications, and non-patent publications cited in any section of this application are herein expressly incorporated by reference in their entirety to the same extent as if each individual patent or publication were specifically and individually indicated to be incorporated by reference.

All of the articles and/or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the articles and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations may be applied to the articles and/or methods and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit and scope of the disclosure. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the disclosure.

The following terms used in accordance with the present disclosure should be understood to have the following meanings unless otherwise indicated.

The words "a" or "an," when used in conjunction with the term "comprising," may mean "one," but is also consistent with the meaning of "one or more," at least one, "and" one or more. The term "or" is used to mean "and/or" unless explicitly stated otherwise only when alternatives are mutually exclusive, although the disclosure supports definitions that refer only to alternatives and to "and/or. Throughout this application, the term "about" is used to mean including variations in the value of a quantitative device, in the inherent error of a method, or in the presence of variations between study objects used to determine the value. For example, but not by way of limitation, when the term "about" is used, the specified value may vary by plus or minus 12%, or 11%, or 10%, or 9%, or 8%, or 7%, or 6%, or 5%, or 4%, or 3%, or 2%, or 1%. The use of the term "at least one" should be understood to include any number of 1 and more than 1, including but not limited to 1,2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term "at least one" may extend to 100 or 1000 or more depending on the term to which it is attached. In addition, the amount of 100/1000 should not be considered limiting, as lower or higher limits may also produce satisfactory results. In addition, use of the term "X, Y and at least one of Z" should be understood to include X alone, Y alone, and Z alone, as well as any combination of X, Y and Z. The use of ordinal number terms (i.e., "first," "second," "third," "fourth," etc.) is merely to distinguish two or more items and are not meant to imply any order, sequence, or importance to one item over another or any order of addition unless otherwise explicitly stated.

As used herein, the words "comprising" (and any form of comprising, e.g., "comprises"), "having" (and any form of having, e.g., "has"), "including" (and any form of including, e.g., "includes") or "containing" (and any form of containing, e.g., "contains") are inclusive or open-ended, and do not exclude additional unrecited elements or method steps. As used herein, the term "or combinations thereof refers to all permutations and combinations of the listed items preceding the term. For example, "A, B, C or a combination thereof" is intended to include at least one of: A. b, C, AB, AC, BC, or ABC, if the order is important in a particular context, then BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations of duplicate items that contain one or more items or terms, such as BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, and the like. Those of skill in the art will understand that there is generally no limitation on the number of items or terms in any combination, unless apparent from the context.

Any reference throughout this specification to "one embodiment" or "an embodiment" means that a particular element, feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrase "in one embodiment" appearing in various places throughout the specification are not necessarily all referring to the same embodiment.

With respect now to specific non-limiting embodiments, the present disclosure includes a granular product for preparing a paint and/or coating formulation comprising, consisting of, or consisting essentially of coarse particles of a Nonionic Synthetic Associative Thickener (NSAT). In one non-limiting embodiment, the NSAT rheology modifier may be selected from the group consisting of hydrophobically modified ethoxylated urethane (HEUR), hydrophobically modified polyacetal polyether (HMPAPE), hydrophobically modified polyethylene glycol (HMPEG), and combinations thereof. In one non-limiting embodiment, the coarse particles of the NSAT rheology modifier have an average particle size of from about 0.5mm to about 5.0mm, and at least about 10 weight percent of the NSAT is retained on a 1.18mm screen (No. 16) as measured according to ASTM C136-06 standard test method for sieve analysis of coarse and fine aggregates.

The granular product may further comprise a dispersant. As used herein, the term "dispersant" refers to any compound or material that effectively wets and separates the particulate product of the present disclosure in a fluid. The dispersing agent may be one or more of a sugar, a salt, silica and a surfactant. In one non-limiting embodiment, the salt may be an organic salt, an inorganic salt, or a salt of a polymer. The term "sugar" as used herein refers to any substance in the class of soluble crystalline carbohydrates, including monosaccharides, disaccharides, oligosaccharides, polysaccharides, and combinations thereof. Non-limiting examples of sugars for use according to the present disclosure may include, but are not limited to, fructose, galactose, glucose, lactose, maltose, sucrose, and combinations thereof. In one non-limiting embodiment, the sugar is sucrose.

In another non-limiting embodiment, the dispersant can be a water-insoluble material such as silica, silicic acid, amorphous aluminosilicates, crystalline aluminosilicates, alumina, clays such as, by way of example only, bentonite, montmorillonite, and bauxite, and combinations thereof.

The dispersant may be a surfactant. The surfactant may be a nonionic or anionic surfactant. Examples of nonionic surfactants may include, but are not limited to: c₁₂-C₁₈Fatty alcohol ethoxylate, C₁₂-C₁₄Fatty alcohol ethoxylate, C₁₆-C₁₈Fatty alcohol ethoxylate, C₁₃-C₁₅Oxoalcohol ethoxylates, C₁₀-C₁₈Alcohol ethoxylate, C₁₃Oxoalcohol ethoxylates, C₁₀Guerbet (Guerbet) alcohol ethoxylate, C₁₀Guerbet alcohol alkoxylates, C₁₀Oxoalcohol ethoxylates, alkyl polyglucosides (e.g., C)₈-C₁₀Alkyl polyglucosides, C₈-C₁₄Alkyl polyglucosides, C₁₂-C₁₄Alkyl polyglucosides, C on inorganic and organic supports₁₂-C₁₀Mixtures of alkyl polyglucosides), amine ethoxylates (e.g., oleylamine +12EO, cocoamine +12 EO), aminopolyols (e.g., triethanolamine +18EO, ethylenediamine +4PO), alkylpyrrolidones (e.g., N-octylpyrrolidone, N-butylpyrrolidone, N-dodecylpyrrolidone), resin precursors and additives (e.g., bisphenol A ethoxylate, BISA +3EO, BISA +4EO, BISA +6EO), emulsifiers and solubilizers (e.g., 4-C of the calcium salt of benzenesulfonic acid)_10-13Secondary alkyl derivatives, castor oil +20EO, castor oil + 35EO, castor oil + 40EO, epoxidized vegetable oils, ethoxylated rapeseed oils, ethoxylated sorbitol esters, decanol +3EO, C₈Fatty alcohol +4EO, fatty alcohol ethoxylate, C₈-C₁₀Fatty alcohol + -5 EO, C₁₂-C₁₄Fatty alcohol +50EO, ethoxylated sorbitan trioleate, castor oil ethoxylate, phenol ethoxylateAlcohol ethoxylates, ethoxylated mono/diglycerides), suds suppressors (e.g., polyalkoxy esters and solvents, fatty alcohol alkoxylates, carboxylic acid esters, phosphoric acid esters, combinations of paraffin and silicon on a carrier, alkyl polyalkylene glycol ethers, guerbet alcohol C₁₆2EO, fatty alcohol alkoxylates), low foaming nonionic surfactants (e.g., fatty alcohol alkoxylates, modified fatty alcohol polyglycol ethers, amine alkoxylates, capped Guerbet alcohol alkoxylates, capped fatty alcohol alkoxylates, PO/EO block copolymers), lauramine oxide, cocamidopropyl amine oxide, alkylamidopropyl betaines, polyglycol ethers of aliphatic glycols, oleamide +10EO, emulsifiable rapeseed methyl oleate, unsaturated fatty alcohol ethoxylates, fatty alcohol polyglycol ethers with fatty acids, unsaturated fatty alcohol ethoxylates), polyethylene glycols, polypropylene glycols, methyl polyethylene glycols, alkyl polyalkylene glycol copolymers, alkyl polypropylene glycols, polyfunctional polyalkylene glycols, reactive polyalkylene glycols.

Other examples of nonionic surfactants can include, but are not limited to, alkylphenol ethoxylates, such as nonylphenol ethoxylates and octylphenol ethoxylates; secondary alcohol alkoxylates, e.g. secondary alcohol ethoxylates (TERGITOL)^TM15-S-9, commercially available from Dow Chemistry Company); and primary alcohol alkoxylates.

Examples of anionic surfactants may include, but are not limited to: sodium lauryl ether sulfate salt +2EO, isotridecyl alcohol ether sulfate sodium salt +20EO, fatty alcohol ether sulfate sodium salt +2EO, fatty alcohol ether sulfate sodium salt +4EO, fatty alcohol ether sulfate sodium salt +7EO, fatty alcohol ether sulfate sodium salt +12EO, fatty alcohol ether sulfate sodium salt +30EO, fatty alcohol ether sulfate sodium salt +50EO, C₁₂-C₁₄Fatty alcohol ether sodium sulfate +1EO, C₁₂-C₁₄Fatty alcohol ether sodium sulfate +2EO, C₁₂-C₁₄Fatty alcohol ether sodium sulfate +3EO, C₈-C₁₄Fatty alcohol ammonium sulfate salt, 2-ethylhexyl sodium sulfate salt, C₁₆-C₁₈Fatty alcohol sulfuric acid sodium salt, C₁₂Fatty alcohol sodium sulfate,C₁₂-C₁₄Fatty alcohol sulfuric acid sodium salt, C₁₂-C₁₆Fatty alcohol sulfuric acid sodium salt, C₁₂-C₁₈Fatty alcohol sulfuric acid sodium salt, C₁₆-C₁₈Fatty alcohol sulfuric acid sodium salt, C₈Fatty alcohol sodium sulfate, Linear C₁₀-C₁₃Sodium salt of alkyl benzene sulfonic acid, Linear C₁₀-C₁₃Sodium alkyl benzene sulfonate and potassium oleate sulfonate.

Other examples of surfactants used in the present disclosure may include, but are not limited to: ester quaternary ammonium salts, alkyl ether phosphate sodium salts, sodium N-lauryl- β -iminodipropionate, acid phosphate esters of fatty alcohol ethoxylates +3EO, monoalkenyl sulfosuccinic acid sodium salts +5EO, diisodecyl sulfosuccinic acid sodium salts, dioctyl sulfosuccinic acid sodium salts, acid phosphate esters, dodecylbenzene sulfonic acid amine salts, alkyl ester phosphates, and the like.

In one non-limiting embodiment, the dispersant may comprise less than 10% surfactant by weight of solids, or less than 1% surfactant by weight of solids, or less than 0.1% surfactant by weight of solids, based on the weight of NSAT. In another non-limiting embodiment, the dispersant is free of surfactant.

The amount of dispersant may be from about 1 to about 15% by weight of solids, or from about 3% to about 14% by weight of solids, or from about 3% to about 10% by weight of solids, or from about 3% to about 5% by weight of solids, based on the weight of NSAT.

In one non-limiting embodiment, the dispersant comprises silica. The silica dispersant has an average particle size of greater than 150nm, or from about 200nm to about 200 μm, or from about 200nm to about 100 μm, or from about 200nm to about 1 μm, or from about 800nm to about 200 μm, or from about 1 μm to about 50 μm, or from about 100 μm to about 200 μm. The amount of silica may be from about 1 to about 15% by weight solids, or from about 3% to about 14% by weight solids, or from about 3% to about 10% by weight solids, or from about 3% to about 5% by weight solids, based on the weight of NSAT. In one non-limiting embodiment, the silica may be hydrophobic silica. Examples of silica may include, but are not limited to, silicon dioxide (S)IPERNAT^TM22s, commercially available from Evonik Corporation USA).

The granular product of the present disclosure can allow for significant reductions in shipping costs and storage volumes, but also allows for lower construction and use costs, allowing for more environmentally friendly packaging materials.

Latex paints are aqueous systems that are typically made by a two-step process. First, the milling or dispersing stage is prepared by mixing the dry paint pigment with other mill phase components, including most other solid powder formulation materials, under constant high shear agitation to provide a high viscosity and high solids content mixture. This part of the process is intended to effectively wet and deagglomerate the dry pigments and stabilize them in the aqueous dispersion. The second step of the paint manufacturing process is often referred to as the letdown or dilution stage because the viscous grind is diluted with the remaining formulation components, which are typically less viscous than the grind mix. Typically, the latex resin, any pre-dispersed pigment, and any other paint materials that require only mixing and may require moderate shear are mixed together in the letdown stage. The letdown stage may be accomplished by sequentially adding the letdown components to a vessel containing the grind mixture, or by adding the grind mixture to a vessel containing a pre-mix of the latex resin and other letdown components, followed by sequentially adding the final letdown components. In either case, constant stirring is required, but without the application of high shear forces. The coarse-grained products of the present disclosure and/or claims may be added at any time during the paint production process.

The term "granular" as used herein means that the ingredients comprising the granular product are in the form of discrete units designated "granules". The particles may have any desired shape. For example, but not by way of limitation, the particles may be substantially spherical, slightly elongated, lamellar, discoidal, and/or combinations thereof. As used herein, the term "flake" is used in a conventional sense and, in general, includes flakes having a length of about 0.5 to about 5.0mm, a width of about 0.5 to about 5.0mm, a thickness of about 0.1 to about 1.5mm or about 0.5 to about 1.2mm, or about 0.5 to about 1.0mm, and an aspect ratio of about 10:1, or about 9:1, or about 8:1, or about 7:1, or about 6:1, or about 5:1, or about 4:1, or about 3:1, or about 2:1, or about 1: 1. In one non-limiting embodiment, the thickness is about 1.0 mm.

The particle size of the coarse-particulate product can be measured by sieve size analysis (ASTM C136-06 Standard test method for Sieve analysis of coarse and fine aggregates). In one non-limiting embodiment, the NSAT has an average particle size of from about 0.5mm to about 5.0mm, and at least about 10% of the NSAT by solid weight is retained on a 1.18mm sieve (No. 16) as measured according to ASTM C136-06 standard test method for sieve analysis of coarse and fine aggregates. In another non-limiting embodiment, the particle size of the NSAT is from about 0.5 to about 4.75mm, or from about 0.5 to about 4.2mm, or from about 0.5 to about 4.0mm, or from about 0.5 to about 3.35mm, or from about 0.5 to about 2.8mm, or from about 0.5 to about 2.36mm, or from about 0.8 to about 4.75mm, or from about 0.8 to about 4.2mm, or from about 0.8 to about 4.0mm, or from about 0.8 to about 3.35mm, or from about 0.8 to about 2.8mm, or from about 0.8 to about 2.36mm, or from about 1.0 to about 4.0mm, or from about 1.0 to about 3.35mm, or from about 1.0 to about 2.8mm, or from about 1.18 to about 4.0mm, or from about 1.18 to about 3.35mm, or from about 1.18 to about 2.8 mm. In another non-limiting embodiment, at least 20% of the particles are retained on a 1.18mm sieve (No. 16), or at least 40% of the particles are retained on a 1.18mm sieve (No. 16), or at least 50% of the particles are retained on a 1.18mm sieve (No. 16), or at least 80% of the particles are retained on a 1.18mm sieve (No. 16), or at least 100% of the particles are retained on a 1.18mm sieve (No. 16). In yet another non-limiting embodiment, less than 5% of the particles remain on a 2.36mm sieve (No. 8).

The rheological properties of aqueous systems can be controlled by the type of NSAT. The NSAT may be selected from the group consisting of hydrophobically modified polyacetal polyether (HMPAPE), hydrophobically modified ethoxycarbamate (HEUR), hydrophobically modified polyethylene glycol (HMPEG), and combinations thereof.

In one non-limiting embodiment, the NSAT has at least one hydrophobic end group. The hydrophobic group may be selected from alkyl, aryl, alkaryl and alicyclic moieties. In one non-limiting embodiment, the hydrophobic group is an alkyl moiety having from about 4 to about 16 carbon atoms, or from about 4 to about 14 carbon atoms, or from about 4 to about 12 carbon atoms, or from about 4 to about 10 carbon atoms, or from about 4 to about 6 carbon atoms.

The NSAT polymer architecture is typically tailored to meet high or low shear rheological requirements. Blending at least one rheology modifier represents a means of using a small set of base rheology modifiers to produce a wide range of customized products tailored to a particular customer paint formulation. Accordingly, the above granular product further comprises an additional rheology modifier, such as at least one cellulose ether. Non-exhaustive examples of cellulose ethers include, but are not limited to: hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), Methyl Cellulose (MC), methyl hydroxyethyl cellulose (MHEC), ethyl hydroxyethyl cellulose (EHEC), methyl hydroxypropyl cellulose (MHPC), and hydrophobically modified derivatives of the above cellulose ethers. In one embodiment, the NSAT may be mixed with additional rheology modifiers to form a mixed rheology modifier. Such mixtures may also contain the previously disclosed dispersants.

The blended rheology modifier may be prepared in the melt phase prior to particle formation or as a dry blend of the individual powder components. In addition to modifying the rheological properties through mixing, other functional ingredients used in paint manufacture can be incorporated into the NSAT rheology modifier particles, thereby simplifying paint manufacture by reducing the amount of material that must be added during paint manufacture. Examples of such functional ingredients include, but are not limited to, dispersants, wetting agents, surfactants, biocides, defoamers, and coalescents.

The granular product can be prepared in a variety of ways well known to those skilled in the art of polymer processing by using equipment. Examples of suitable equipment may include, but are not limited to, spray dryers, pan granulators, drum flakers, and mills. The particular method used will depend on the synthetic method used to produce the NSAT rheology modifier as well as the particle size requirements.

The NSAT rheology modifier particles can also be coated with other rheology modifiers such as cellulose ethers or functional ingredients. In addition, the NSAT rheology modifier particles can also be coated with hydrophobic, hydrophilic, and/or amphiphilic polymers, if desired. This coating step may be accomplished by any conventional method, such as spray drying and the like.

The present disclosure relates to aqueous coating compositions comprising a film-forming polymer and the aforementioned specific products. In one non-limiting embodiment, the film-forming polymer may be a latex used in the preparation of aqueous paints. Generally, aqueous paints (latex paints) are paints in which a film-forming polymer is dispersed in a solvent in the form of small insoluble resin particles (colloidal and coarse dispersions). Film-forming polymers may include, but are not limited to, polyvinyl acetate, styrene-butadiene copolymers, acrylics, polystyrene, and alkyds. The aqueous coating composition may further comprise one or more other ingredients including, but not limited to, coalescents, solvents, wetting agents, defoamers, matting agents, dispersants, thickeners, biocides, mildewcides, pigments, and surfactants. The aqueous coating composition may comprise from about 0.1 wt% to about 5 wt%, or from about 0.4 wt% to about 5 wt%, or from about 0.5 wt% to about 3 wt%, or from about 1 wt% to about 3 wt%, of the particulate product, based on the total weight of the aqueous coating composition. In one non-limiting embodiment, the aqueous coating composition can comprise a paint.

The present disclosure also includes a method of preparing an aqueous coating composition, the method comprising the steps of: (1) adding a film-forming polymer to the aqueous solution; (2) the particulate product comprising coarse particles of the NSAT rheology modifier is added to an aqueous solution to form the aqueous coating composition. In one non-limiting embodiment, the granular product further comprises a dispersant.

In one non-limiting embodiment, the particulate product is added to the aqueous solution prior to adding the film-forming polymer to the aqueous solution. Specifically, the method comprises the following steps: a) obtaining the aforementioned granular product; b) adding the granulated product to an aqueous solution in the absence of a film-forming polymer to obtain a mixture; and c) adding the film-forming polymer to the mixture until the particulate product is dissolved.

In another non-limiting embodiment, the particulate product is added to the aqueous solution after the film-forming polymer is added to the aqueous solution. The film-forming polymer can be added to the aqueous solution by, for example, but not limited to, dispersing or emulsifying the polymer in the aqueous solution. Specifically, the method comprises the following steps: a) obtaining the aforementioned granular product; b) the granular product and the aqueous solution with the film-forming agent are mixed until the granular product is dissolved.

In another non-limiting embodiment, the particulate product is added to the aqueous solution at the same time the film-forming polymer is added to the aqueous solution.

The following examples illustrate the presently disclosed and claimed inventive concepts, parts and percentages being by weight unless otherwise indicated. Each embodiment is provided by way of explanation of, and not limitation of, the presently disclosed and claimed inventive concepts. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed and claimed inventive concept without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment. Thus, it is intended that the disclosed and claimed inventive concepts cover such modifications and variations as fall within the scope of the appended claims and their equivalents.

Examples

Polymer synthesis

₁₆Example 1: C-HMPAPE

To an Abbe ribbon mixer was added polyethylene glycol [ PEG-8000, MW about 8000g/mol (1250g) ] and sodium hydroxide (NaOH) (37g) to form a PEG-800/NaOH mixture. After sealing the mixer, the mixture was heated at about 80 ℃ for about one (1) hour. Dibromomethane (18.5g) was then added to the PEG-8000/NaOH mixture and the resulting reaction mixture was heated at about 80 ℃ for about 4 hours to form a PEG-8000/methylene copolymer.

To the PEG-8000/methylene copolymer was added 1-bromohexadecane (65g) as an envelope at about 80 deg.CA terminating agent, and heating the resulting reaction mixture at about 120 ℃ for about two (2) hours. The mixer was then opened and the molten reaction mixture was poured into a plastic tray. After cooling to 20-25 ℃ the reaction mixture solidifies to obtain C₁₆End-capped polyacetal polyethers (C)₁₆HMPAPE) sample.

₁₂Example 2: C-HMPAPE

Preparation of C according to example 1 using 1-bromododecane (70g) as end-capping agent₁₂-HMPAPE sample.

₆Example 3: C-HMDI-HEUR

PEG-8000[ MW about 8000g/mol (1250g) ] was dried by heating at about 120 ℃ while mixing under vacuum in a batch melt reactor for about one (1) hour. The mixture was cooled to about 85 ℃. Hexanol (34.4g) was then added and mixed for about five (5) minutes. 4, 4' -methylenebis (cyclohexyl isocyanate) (HMDI) (134.6g) was then added and mixed for about five (5) minutes. Dibutyltin dilaurate (DBTDL) (3.2g) was then added and the resulting reaction mixture was heated from about 85 ℃ to about 115 ℃ for about two (2) hours while mixing. After about two (2) hours, the resulting molten polymer was removed from the reactor and cooled to give HEUR polymer as a white solid.

Powder preparation

Example 4: type 1

Each of the solid polymers from examples 1-3 was ground in a Waring Professional Electric Spice Grinder (Professional Electric Spice Grinder). The ground material was sieved between stacked ASTM E-118 mesh (2.38mm) and 16 mesh (1.18mm) screens, thus representing a particle size of between 1.18 and 2.38mm (measured according to ASTM C136-06 standard test method for sieve analysis of coarse and fine aggregates). After grinding, the polymer was mixed with 3%22S silica (Evonik Corporation). The resulting powder mixture was used for testing.

Example 5: type 2

The solid polymer from example 1 was ground in a Waring professional electric spice mill. The ground material was sieved between stacked ASTM E-118 mesh (2.38mm) and 20 mesh (0.84mm) screens, thus representing a particle size of between 0.84 and 2.38mm (measured according to ASTM C136-06 standard test method for sieve analysis of coarse and fine aggregates). After grinding, the polymer was mixed with 3%22S silica (Evonik Corporation). The resulting powder mixture was used for testing.

Example 6: type 3

The solid polymer of example 2 was flaked using a 6 "x 8" single drum flaker with a stainless steel drum and stainless steel applicator roll. The sheet material was ground in a Waring professional electric spice mill. The ground material was sieved between stacked ASTM E-118 mesh (2.36mm) and 16 mesh (1.18mm) screens, with at least about 50% polymer by solids weight retained on the 1.18mm screen (measured according to ASTM C136-06 standard test method for sieve analysis of coarse and fine aggregates). After grinding, the polymer was mixed with 3%22S silica (Evonik Corporation). The resulting powder mixture was used for testing.

Example 7: type 4

Type 4 polymer was prepared using the same procedure as example 6 without addition of silica. The ground material was sieved between stacked ASTM E-118 mesh (2.36mm) and 16 mesh (1.18mm) screens, with at least about 50% polymer by solids weight retained on the 1.18mm screen (measured according to ASTM C136-06 standard test method for sieve analysis of coarse and fine aggregates). The resulting powder containing no silica was used for testing.

Dissolution test

To illustrate the improvement in dissolution characteristics resulting from the addition of various additives, the samples obtained from the foregoing examples were subjected to a water dissolution test and a paint dissolution test.

Water dissolution test

Water dissolution was monitored using a fluke in combination with a HAAKE VT500 viscometer. Each of the powder samples obtained from the previous examples was dissolved in a certain amount in tris buffer at pH 8.0 to make 1 wt%, 2 wt%, and 5 wt% solutions, respectively. The solution was mixed at 500rpm for about one (1) hour. Torque data was collected over time, which is similar to dissolution over time, in that torque is related to solution viscosity build, which is dependent on dissolution of the rheology modifier. Figures 1-5 depict dissolution data for different samples in the above examples. Table 1 summarizes the results of the water solubility test in figures 1 to 5.

TABLE 1 Water dissolution results

Paint dissolution test

Example 8

Paint dissolution was monitored using marine propeller blades in combination with a HAAKE VT500 viscometer. Dissolution was carried out in an 8 oz jar containing the acrylic latex-based 70PVC paints listed in table 2.

TABLE 2.70 PVC acrylic-based paints

(1) A 20% dipropylene glycol aqueous solution of 1, 2-benzisothiazolin-3-one commercially available from Arch Chemicals, inc.

(2) Dispersants, commercially available from the Dow Chemical Company.

(3) Nonylphenoxy branched poly (ethyleneoxy) ethanol, commercially available from Solvay s.a.

(4) Nonionic ethoxylated nonylphenols, commercially available from Solvay s.a.

(5) 2-amino-2-methyl-1-propanol, commercially available from Angus Chemical Company.

(6) Foam control agents, commercially available from Ashland LLC.

(7) Thermokalite treated diatomaceous earth, commercially available from Sigma-Aldrich.

(8) Rutile titanium dioxide, commercially available from The Chemours Company.

(9) Layered spray dried kaolin, commercially available from BASF Corporation.

(10) Vinyl acrylic latex, commercially available from Nexeo Solutions.

(11) Ester alcohols, commercially available from Eastman Chemical Company.

(12) Hydrophobically modified hydroxyethylcellulose, commercially available from Ashland LLC.

The ingredients of table 2 were mixed to form a mixture, with the exception of Natrosol, type 3 and water listed in the letdown stage. Natrosol and water were added to the mixture. Type 3 solids were then added. Torque data was collected over time. A comparison of the dissolution characteristics of type 3 powder in paint at 300rpm and 500rpm is shown in figure 6. At the end of the dissolution study (one hour), the KU and ICI viscosities of the resulting paints were measured to be 109KU/2.3P and 109.8KU/2.3P for the samples mixed at 300 and 500rpm, respectively.

Paint thickening test

Paint thickening tests using the samples of the previous examples were conducted using a 31PVC small particle size acrylic latex paint formulation.

Example 9

The paints were made using the formulations listed in the table below. First, dried C of type 3 and type 1₁₆The HMPAPE samples were added separately to water at 15.21 wt% of the formulation. After the paint manufacturing process, the paint obtained was creamy and smooth with no detectable insoluble particles. The KU and ICI of the resulting paints were determinedThe viscosity was 96.8KU and 0.90P ICI.

(1) Potassium salts of phosphoric acid co-esters of aliphatic alcohols, commercially available from Ashland LLC.

(2) Phosphate ester surfactant, commercially available from Ashland LLC.

(3) Foam control agents, commercially available from Ashland LLC.

(4) Aqueous dispersions of 1, 2-benzisothiazolin-3-one, commercially available from Ashland LLC.

(5) Inert, gel grade attapulgite, commercially available from BASF Corporation.

(6) Rutile titanium dioxide, commercially available from Tronox Limited.

(7) Calcium aluminum silicate, commercially available from Burgess Pigment.

(8) Micronized functional filler, commercially available from The Cary Company.

(9) Acrylic adhesives, commercially available from the Dow Chemical Company.

(10) A40% aqueous dispersion of 3-iodo-2-propynyl butylcarbamate, commercially available from Troy Corporation.

Example 10

The paints were made using the formulations listed in the table below. First, a dry type 3 sample was added to water at 15.21% by weight of the formulation, and a paint formulation was made according to the method described above. Added at the end of the paint manufacturing processNLS220 (0.77% by weight) to produce a paint with a viscosity of 103.3KU and 1.035P ICI. The paint obtained was creamy and smooth with no detectable insoluble particles.

(1) Nonionic synthetic associative thickeners, commercially available from Ashland LLC.

Example 11

The paints were made using the formulations listed in the table below. First, type 1C is dried₁₆The HMPAPE sample was added to water at 15.21% by weight of the formulation and the paint formulation was made according to the method described above. Added at the end of the paint manufacturing processNHS300 to produce a paint with a viscosity of 105KU and 1.18P ICI. The paint obtained was creamy and smooth with no detectable insoluble particles.

(1) Nonionic synthetic associative thickeners, commercially available from Ashland LLC.

Example 12

First, dry type 4 was added to 15.21% by weight of the formulation in water and a paint formulation was prepared according to the method described above. Added at the end of the paint manufacturing processNLS220 to produce a paint with viscosity of 104KU and 1.033P ICI. The paint obtained was creamy and smooth with no detectable insoluble particles.