阅读说明：本技术 通用溶剂型颜料分散体树脂 (Universal solvent-borne pigment dispersion resins ) 是由 迈克尔·D·科德 亚伦·M·帕尔默 卡特里娜·A·香珀特 佩吉·L·斯特菲 菲利普·J·鲁霍 于 2018-02-08 设计创作，主要内容包括：本申请涉及衍生自(甲基)丙烯酸异冰片酯和一种或多种其他单体的共聚颜料分散体树脂,该共聚物颜料分散体树脂的数均分子量小于约10000,并且衍生自足够的(甲基)丙烯酸异冰片酯,使得在室温下与至少三倍树脂重量的无味矿物油精结合时,60重量％的在丙二醇单甲醚乙酸酯中的树脂溶液形成澄清溶液。该树脂可以与基于极性或非极性溶剂的溶剂型涂料组合物相容地混合,并且可以提供单一的工厂着色剂或销售点着色剂配方,用于调色多种此类涂料组合物。(The present application relates to a copolymeric pigment dispersion resin derived from isobornyl (meth) acrylate and one or more other monomers, the copolymeric pigment dispersion resin having a number average molecular weight of less than about 10000 and being derived from sufficient isobornyl (meth) acrylate such that when combined with an odorless mineral spirit of at least three times the weight of the resin at room temperature, a 60 weight percent solution of the resin in propylene glycol monomethyl ether acetate forms a clear solution. The resin can be compatibly mixed with solvent-borne coating compositions based on polar or non-polar solvents, and can provide a single factory colorant or point of sale colorant formulation for tinting a plurality of such coating compositions.)

1. A pigment dispersion resin comprising a copolymer comprising monomer units derived from isobornyl (meth) acrylate and one or more other monomers, wherein the copolymer has a number average molecular weight (Mn) of less than about 10000 and is derived from sufficient isobornyl (meth) acrylate such that, when combined with an odorless mineral spirit of at least three times the weight of the copolymer at room temperature, a solution of 60% by weight of the copolymer in propylene glycol monomethyl ether acetate forms a clear solution.

2. A pigment vehicle for use in a factory or a colorant for use at a point of sale, the pigment vehicle or colorant comprising one or more pigments and optionally a polar or non-polar non-aqueous solvent in the pigment dispersion resin of claim 1.

3. A coating composition comprising a dispersion of one or more pigments in a solution or dispersion comprising a film-forming binder resin, a polar or non-polar non-aqueous solvent, and the pigment dispersion resin of claim 1.

4. A point-of-sale system comprising a plurality of base coating compositions and a compatible colorant array, said coating compositions comprising at least one coating composition comprising a film-forming binder resin and a polar non-aqueous solvent and at least one coating composition comprising a film-forming binder resin and a non-polar solvent; and the colorant array comprises at least one pigment-containing white, black, red, blue, and green colorant, optionally a polar or non-polar non-aqueous solvent, and the pigment dispersion resin of claim 1.

5. A point-of-sale method for tinting a coating composition, comprising the steps of: tinting a plurality of base coating compositions using an array of tinting colorants, wherein each tinting colorant comprises a pigment, a copolymer, and optionally a polar or non-polar non-aqueous solvent, the plurality of base coating compositions comprising at least one coating composition comprising a film-forming binder resin and a polar non-aqueous solvent and at least one coating composition comprising a film-forming binder resin and a non-polar solvent, wherein the array comprises at least white, black, red, blue, and green tinting colorants, each tinting colorant comprising the pigment dispersion resin of claim 1.

6. A method for making a coating composition comprising the step of combining a carrier liquid, a binder resin, and a pigment vehicle, wherein the pigment vehicle comprises a plurality of pigment particles and the pigment dispersion resin of claim 1.

7. A method for making a pigment dispersion resin comprising the steps of: providing isobornyl (meth) acrylate and one or more other free radically polymerizable monomers dissolved in a solvent, preferably in the presence of a chain transfer agent, and copolymerizing the monomers to form a copolymer having an Mn of less than about 10000 and derived from sufficient isobornyl (meth) acrylate such that a solution of 60 weight percent of the copolymer in propylene glycol monomethyl ether acetate forms a clear solution when combined with at least three times the weight of the copolymer of odorless mineral spirits at room temperature.

8. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer comprises monomer units having a majority by weight derived from isobornyl (meth) acrylate.

9. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer comprises monomer units derived from methyl (meth) acrylate, one or more of butyl (meth) acrylate or styrene, and isobornyl (meth) acrylate.

10. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer comprises greater than about 55 wt% of monomer units derived from isobornyl (meth) acrylate and has a Mn of less than or equal to about 3000.

11. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer comprises monomer units derived from isobornyl (meth) acrylate in an amount greater than about 70 weight percent.

12. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer comprises monomer units derived from isobornyl (meth) acrylate in an amount greater than about 75 weight percent and monomer units derived from methyl (meth) acrylate in an amount greater than about 20 weight percent.

13. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer comprises monomer units derived from methyl (meth) acrylate in an amount greater than about 5% by weight and monomer units derived from styrene in an amount greater than about 25% by weight.

14. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer is substantially free of hydrophilic functional groups derived from monomers other than isobornyl (meth) acrylate and methyl (meth) acrylate.

15. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the clear solution remains even if an odorless mineral spirit is added to a 60 weight percent copolymer solution in an amount of at least four times the weight of the copolymer.

16. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any one of claims 5 to 7, wherein the clear solution remains even if an odorless mineral spirit is added to a 60 weight percent copolymer solution in an amount of at least six times the weight of the copolymer.

17. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer is substantially completely soluble in an odorless mineral spirit.

18. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer is substantially completely soluble in ketones, acetates, and aromatic solvents.

19. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any one of claims 5 to 7, wherein the copolymer is capable of achieving high pigment loadings providing a desired flow for a pigment vehicle or colorant exhibiting or approaching newtonian behavior.

20. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer has a polydispersity of at least about 1.8.

21. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer has a polydispersity of at least about 2.

22. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer has a glass transition temperature greater than 25 ℃.

23. The pigment dispersion resin of claim 1, the pigment vehicle or colorant of claim 2, the coating composition of claim 3, the point-of-sale system of claim 4, or the method of any of claims 5 to 7, wherein the copolymer has a glass transition temperature greater than 40 ℃.

Technical Field

The present disclosure relates to pigment dispersion resins for the manufacture or tinting of paints and other coating compositions.

Background

The coating composition may comprise a color imparted by the pigment particles. Pigments may be added at a coating composition manufacturing facility where large batches (e.g., typically 50 liters or more) may be manufactured in one or more standard pre-mixed colors. It is also possible to add colorants containing pigments to one or more base coating compositions at point-of-sale dispensing points (point-of-sale) using a volumetric colorant dispensing device and a shaking mixing device to produce small batches (e.g., typically less than 50 liters) of custom-tinted coating compositions in a color array that is much larger than the limited color array available in the pre-mix product.

Several years ago, pigmented coating compositions were virtually all solvent borne. Today, a large proportion of these materials are aqueous. However, in certain end-use applications, many solvent-borne coating compositions are necessary or preferred, and may still be necessary or preferred for a long future.

In the retail paint business, so-called "universal colorants" have been developed for point-of-sale tinting equipment. These point-of-sale universal colorants are typically formulated by modifying the aqueous colorant formulation to include a suitable surfactant, and optionally a suitable dispersant or cosolvent, so that the colorant can be tinted for either aqueous or solvent-borne base paints or stains using the same tinting machine.

Summary of The Invention

The point-of-sale universal colorants described above are typically added to only a few solvent-borne coating compositions (e.g., medium oil alkyds, long oil alkyds, and oil-based stains, and are commonly used in architectural or consumer applications for coating or staining wood). However, such point-of-sale universal colorants are primarily used to tint aqueous coating compositions, such as latex paints. Since latex paints typically account for over 80% of the total amount of paint provided by retail paint stores, universal colorants are typically formulated to optimize their performance in such aqueous systems. Point-of-sale universal colorants may have somewhat less than optimal performance in solvent-based systems, e.g., they may provide poor pigment dispersion or poor toning film performance as compared to specialized point-of-sale colorants used only in solvent-based systems.

Coating composition manufacturers typically manufacture a variety of other solvent-borne coating compositions that may be poorly compatible or incompatible with such point-of-sale universal colorants. Such other solvent-borne coating compositions may include, for example, industrial metal coatings such as epoxy, urethane and short oil alkyds (typically containing non-aqueous carrier liquids with polar character), and compositions for industrial coating or wood staining such as medium and long oil industrial alkyds and stains (typically containing carrier liquids with non-polar character such as odorless mineral spirits). These other solvent-borne coating compositions, whether mixed with pigments at the manufacturing facility or at the point of sale, are typically pigmented or tinted with separately formulated pigment dispersions whose composition depends on the binder, carrier liquid, and in some cases even the desired final color selected. For example, when preparing many pigmented solvent-based coating compositions, the pigment particles are typically blended with a dispersion resin dissolved in a solvent to prepare a pigment vehicle. The pigment vehicle is then blended with the binder, carrier liquid, and other components to form the desired coating composition. The dispersion resin must generally be compatible with the carrier liquid. When preparing a coating composition using an odorless mineral spirit as the carrier liquid, for example, it may be necessary to use a pigment vehicle that contains a dispersion resin that is different from the pigment dispersion resin used in coating compositions containing a polar carrier liquid.

Many known acrylic-based dispersion resins are soluble in solvents such as water, ketones, acetates or aromatics, but are insoluble or have limited solubility in mineral spirits. For example, commercial dispersion resins, such as Paralottm DM-55 from the Dow chemical company, LAROPAL from the Pasteur company^TMA81 and Dianal TB-219 from Dial America, Inc., each is soluble in certain conventional solvents but has limited solubility in odorless mineral spirits (CASNO. 68551-17-7). The extent to which dispersion resins are soluble in odorless mineral spirits appears to provide a useful criterion indicating the compatibility of such dispersion resins with a variety of different polymers or resin systems, and their effectiveness or flexibility in dispersing pigments in a variety of such systems.

It is desirable to provide a pigment dispersion resin that is compatible with both the polar carrier liquid and the mineral spirits. Such pigment dispersion resins would enable coating composition manufacturers (e.g., paint manufacturers) to use the same pigment dispersion resin in many types of solvent-borne coating compositions, including coating compositions with polar carrier liquids and coating compositions with non-polar carrier liquids. This can simplify the in-factory production process for such manufacturers, and can also provide a more flexible or more powerful array of point-of-sale colorants to tint solvent-based coating compositions at retail stores. The resulting pigment dispersion resin may be referred to as a "universal solvent pigment dispersion resin" and is believed to represent a new product category. It should be kept in mind that such dispersion resins represent different end uses and different products than the point-of-sale universal colorants described above, as they do not need to perform well in aqueous systems.

In one aspect, the present invention provides a pigment dispersion resin comprising a copolymer comprising monomer units derived from isobornyl (meth) acrylate and one or more other monomers, wherein the copolymer has a number average molecular weight (Mn) of less than about 10000 and is derived from sufficient isobornyl (meth) acrylate such that, when combined with an odorless mineral olein of at least three times the weight of the copolymer at room temperature, 60% by weight of the copolymer is in propylene glycol monomethyl ether Acetate ("PM Acetate", CH)₃CO₂CH(CH₃)CH₂OCH₃The solution in CAS No.108-65-6) formed a clear solution.

The disclosed copolymers have substantial or complete solubility in both polar solvents (e.g., ketones, acetates, and polar aromatic liquids) and non-polar solvents (e.g., odorless mineral spirits). Without intending to limit the invention to a particular theory of operation, it is believed that various aspects or areas of the disclosed copolymers can provide pigment dispersion resins that have polar and non-polar characteristics that facilitate dissolution of the copolymers in a wide range of polar and non-polar solvents. These aspects or domains may be provided at least in part by the isobornyl (meth) acrylate monomers described, i.e., by isobornyl acrylate (IBA) or isobornyl methacrylate (IBMA), which have structures I and II, respectively, shown below:

in another aspect, the invention provides a pigment vehicle for use in a factory or a colorant for use at a point of sale, the pigment vehicle or colorant comprising a dispersion of one or more pigments in the above copolymer, and optionally a polar or non-polar non-aqueous solvent.

In another aspect, the present invention provides a coating composition comprising a dispersion of one or more pigments in a solution or dispersion comprising the above copolymer, a film-forming binder resin, and a polar or non-polar non-aqueous solvent.

In another aspect, the invention provides a point of sale system comprising a plurality of base coating compositions comprising at least one coating composition comprising a film-forming binder resin and a polar coating non-aqueous solvent and at least one coating composition comprising a film-forming binder resin and a non-polar solvent, and a compatible array of colorants comprising at least white, black, red, blue and green colorants comprising a pigment, the above-described copolymer, and optionally a polar or non-polar non-aqueous solvent.

In another aspect, the present invention provides a point of sale method for tinting a coating composition, the method comprising the steps of: tinting a plurality of base coating compositions using an array of tinting colorants, each tinting colorant comprising a pigment, a copolymer and optionally a polar or non-polar non-aqueous solvent, the plurality of base coating compositions comprising at least one coating composition comprising a film-forming binder resin and a polar non-aqueous solvent and at least one coating composition comprising a film-forming binder resin and a non-polar solvent, wherein the array comprises at least white, black, red, blue and green tinting colorants, each tinting colorant comprising a copolymer comprising monomer units derived from isobornyl (meth) acrylate and one or more other monomers, wherein the copolymer has a number average molecular weight (Mn) of less than about 10000 and is derived from sufficient isobornyl (meth) acrylate such that, when combined with an odorless mineral spirit of at least three times the weight of the copolymer at room temperature, a solution of 60 wt% of the copolymer in propylene glycol monomethyl ether acetate formed a clear solution.

In another aspect, the present invention provides a method for making a coating composition, the method comprising the step of combining a carrier liquid, a binder resin, and a pigment vehicle, wherein the pigment vehicle comprises a plurality of pigment particles and the above-described pigment dispersion resin. In one embodiment, the disclosed method includes using a single such pigment vehicle to produce a plurality of coating compositions, including at least one coating composition comprising a film-forming binder resin and a polar non-aqueous solvent and at least one coating composition comprising a film-forming binder resin and a non-polar solvent.

In another aspect, the present invention provides a method for producing a pigment dispersion resin, the method comprising the steps of: providing isobornyl (meth) acrylate and one or more other free radically polymerizable monomers dissolved in a solvent, preferably in the presence of a chain transfer agent, and copolymerizing the monomers to form a copolymer having an Mn of less than about 10000 and derived from sufficient isobornyl (meth) acrylate such that a solution of 60 weight percent of the copolymer in propylene glycol monomethyl ether acetate forms a clear solution when combined with at least three times the weight of the copolymer of odorless mineral spirits at room temperature.

In certain embodiments, the disclosed pigment dispersion resins are copolymers comprising a majority by weight of monomer units derived from isobornyl (meth) acrylate. In a further embodiment, the disclosed pigment dispersion resin is a copolymer comprising monomer units derived from one or more of methyl (meth) acrylate, butyl (meth) acrylate, or styrene, and isobornyl (meth) acrylate. In a further embodiment, the disclosed pigment dispersion resin is a copolymer comprising greater than about 55 weight percent of monomer units derived from isobornyl (meth) acrylate and having an Mn of less than or equal to about 3000. In certain embodiments, the disclosed pigment dispersion resins can achieve high pigment loadings, providing pigment vehicles or colorants with desirable flow properties that exhibit or approach newtonian behavior.

Drawings

In the drawings, fig. 1 shows an evaluation of a pigment vehicle prepared using a commercially available pigment dispersion resin (upper row) and an exemplary resin of the present invention (lower row). FIG. 1 is adapted from a color photograph, and FIG. 1 shows the original color of the composition.

Detailed Description

The recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

The terms "a", "an", "at least one", and "one or more" are not used interchangeably. Thus, for example, a coating composition containing an additive means that the coating composition includes "one or more" additives.

The term "architectural paint" refers to a coating composition for interior or exterior architectural elements and includes paints and stains.

The term "binder" refers to a natural or synthetic film-forming polymer suitable for use in paints or other coating compositions.

The term "copolymer" refers to a polymer derived from two or more different monomers.

The terms "(meth) acrylate" and "(meth) acrylic acid" refer to acrylate and methacrylate compounds, respectively, as well as acrylic acid and methacrylic acid.

The term "paint" refers to a coating composition comprising a pigment and a film-forming binder that, when applied to a freshly sanded smooth wood surface to form a thin (e.g., 100 μm) wet film thickness of the coating film, dries to form a continuous film on the surface, and contains an impermeable or other stain that dries to form such a continuous film.

The term "pigment" refers to an inorganic particulate material having light reflective properties as well as surface energy and particle size suitable for use in paints and other coating compositions.

The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

The term "solvent-borne" when used with respect to paints or other coating compositions refers to a mixture of the primary liquid vehicle or carrier for such coating compositions that is a non-aqueous or non-aqueous solvent.

The term "aqueous" when used with respect to paints and other coating compositions means that the primary liquid vehicle or carrier for such coating compositions is water.

The disclosed pigment dispersion resins typically comprise a copolymer comprising monomer units derived from isobornyl (meth) acrylate and monomer units derived from monomers other than isobornyl (meth) acrylate. In a preferred embodiment, the monomer units derived from isobornyl (meth) acrylate are present in a majority by weight, for example, may be present in an amount greater than about 50%, greater than about 55%, greater than about 60%, greater than about 65%, greater than about 70%, greater than about 75%, or greater than about 80% based on the weight of the monomers used to prepare the copolymer. In other embodiments, the monomer units derived from isobornyl (meth) acrylate may be present in an amount of less than about 99%, less than about 95%, less than about 90%, or less than about 85%, for example, based on the weight of the monomers used to prepare the copolymer. In some exemplary embodiments, the monomer units derived from isobornyl (meth) acrylate are present in an amount from about 80 weight percent to about 90 weight percent.

Exemplary monomer units other than isobornyl (meth) acrylate that may be used to prepare the disclosed copolymers include free-radically polymerizable monomers such as methyl (meth) acrylate, styrene, butyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, meth) acrylic acid, vinyl acetate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, steryl (meth) acrylate, lauryl (meth) acrylate, and α -methyl-styrene the copolymers may, for example, comprise additional monomer units in a total amount of greater than about 1%, greater than about 5%, greater than about 10%, greater than about 15%, greater than about 20%, greater than about 25%, greater than about 30%, or greater than about 40% by weight based on the weight of the monomers used to make the copolymer, in some embodiments the copolymers may, for example, comprise additional monomer units in a total amount of up to about 55%, up to about 50%, less than about 50%, or less than about 45%, based on the weight of the monomers used to make the copolymer, when more than one such additional monomer units are present, such as isobornyl acrylate, 75: 70, 75: 80, such as 20: 70, 75: 80, or 70: 80, when more than two such monomers are present.

Various blends of the foregoing monomers can be used, and a number of copolymeric resins can be prepared in accordance with the foregoing. In general, it is preferred to prepare the copolymer resin using monomer units derived from isobornyl (meth) acrylate and other monomers suitable for providing a combination of regions having polar characteristics (e.g., hydrophilic groups) and regions having non-polar characteristics (e.g., alkyl or aryl groups) within the copolymer. For example, in some exemplary embodiments, the monomer units derived from methyl (meth) acrylate or butyl (meth) acrylate may be present in the resin in an amount greater than about 5 weight percent, and the monomer units derived from styrene may be present in the resin in an amount greater than about 25 weight percent. In some exemplary embodiments, the monomer units derived from isobornyl (meth) acrylate may be present in the resin in an amount greater than about 75 weight percent, and the monomer units derived from methyl (meth) acrylate or butyl (meth) acrylate may be present in the resin in an amount up to about 25 weight percent. In some embodiments, the monomer units derived from isobornyl (meth) acrylate and the monomer units derived from butyl (meth) acrylate may be present in the resin in an amount greater than about 55 wt.%, greater than about 60 wt.%, greater than about 65 wt.%, greater than about 70 wt.%, greater than about 75 wt.%, or greater than about 80 wt.%. In some embodiments, the copolymer may be substantially free of hydrophilic functional groups derived from monomers other than isobornyl (meth) acrylate, methyl (meth) acrylate, and butyl methacrylate.

The Mn value of the disclosed copolymers is less than about 10000. In some embodiments, the Mn value of the copolymer is less than about 7000, less than about 5000, less than about 3000, less than about 2500, less than about 2000, less than about 1500, or less than about 1000. The number average molecular weight values can be measured using gel permeation chromatography and polystyrene standards and calculated using equation I shown below:

Mn＝(∑N_iM_i)/∑N_iI

where Mi is the molecular weight of the polymer chains of the copolymer and Ni is the number of chains of molecular weight Mi in the copolymer. Additionally, the disclosed copolymers can have a weight average molecular weight (Mw) value of less than about 20000. In some embodiments, the Mw value of the copolymer is less than about 14000, less than about 10000, less than about 6000, less than about 5000, less than about 4000, less than about 3000, or less than about 2000. The weight average molecular weight value can be measured using light scattering techniques and calculated using equation II shown below:

Mw＝(∑N_iM_i ²)/(∑N_iM_i) II

where Mi is the molecular weight of the polymer chains of the copolymer and Ni is the number of chains of molecular weight Mi in the copolymer. In general, as the Mn and Mw values of the copolymers decrease, the resistance of the odorless mineral spirits of the disclosed copolymers will tend to increase. In addition, the viscosity and pigment dispersability of the disclosed copolymers will tend to decrease as the Mn and Mw values of the copolymers increase, with Mn values above about 10000 and Mw values above about 20000 generally being very unsuitable for pigment dispersion. However, copolymers having such higher Mn and Mw values may be used to modify certain binder resins, for example, to alter the adhesion of the binder resin to chalk or other low adhesion surfaces.

The disclosed copolymers can have a variety of polydispersity values, where polydispersity is determined by dividing Mw by Mn. For example, the solubility of the disclosed copolymers in a wide range of polar and non-polar solvents can vary based in part on polydispersity values. In some embodiments, the disclosed copolymers can have a polydispersity of at least 1.7, greater than 1.7, at least about 1.8, at least about 1.9, or at least about 2. In some embodiments, the disclosed copolymers can have a polydispersity of less than about 6, less than about 5, less than about 4, or less than about 3.

As noted above, the disclosed copolymers are derived from sufficient isobornyl (meth) acrylate such that when combined with at least three times the weight of the copolymer of odorless mineral olein at room temperature, a solution of 60 weight percent of the copolymer in PM acetate forms a clear solution. In a preferred embodiment, even larger amounts of odorless mineral olein can be added to the disclosed 60 wt% copolymer solution, and the clear solution will disappear. For example, a clear solution preferably remains even after an odorless mineral olein is added to the 60 wt.% copolymer solution in an amount of at least 4 times, at least five times, at least six times, at least seven times, at least eight times, at least nine times, or at least ten times the weight of the copolymer. In a particularly preferred embodiment, even if an unlimited amount (i.e., any amount) of the flavorless mineral olein is added to the disclosed 60 wt.% copolymer solution, a clear solution will remain, so to speak, the copolymer is substantially completely dissolved in the flavorless mineral olein.

The disclosed resins preferably have a glass transition temperature (Tg) greater than about 25 ℃, more preferably greater than about 30 ℃, and most preferably greater than about 40 ℃. Tg values can be measured using Differential Scanning Calorimetry (DSC) and can be calculated using the Fox equation. For example, the theoretical Tg of a copolymer made from two monomer feeds can be calculated using equation III below:

1/Tg＝Wa/Tga+Wb/Tgb

wherein Tga and Tgb are the glass transition temperatures of homopolymers made from monomers "a" and "b", respectively; and is

Wa and Wb are the respective weight fractions of the copolymers "a" and "b".

Generally, the Tg can be increased by increasing the proportion of IBA (homopolymer with a Tg of 94 ℃), IBMA (homopolymer with a Tg of 110 ℃), or other high Tg monomers. Exemplary other such monomers include methyl methacrylate (homopolymer Tg of 105 ℃. about.120 ℃), t-butyl methacrylate (homopolymer Tg of 118 ℃), styrene (homopolymer Tg of 100 ℃), and various substituted styrenes. The fouling resistance of coating compositions comprising the disclosed copolymers will tend to increase with decreasing Tg values.

In some embodiments, the invention includes a method of making the disclosed copolymers, generally comprising the steps of: isobornyl (meth) acrylate and one or more other free-radically polymerizable monomers dissolved in a solvent are provided, preferably in the presence of a chain transfer agent, and the monomers are copolymerized to form a copolymer. Providing the monomer dissolved in the solvent may include a process including actively dissolving the monomer in the solvent or providing a previously prepared monomer solution dissolved in the solvent. The chain transfer agent may be added to the solvent before, after, or during any one or more of the dissolution of the monomer in the solvent. The method may further comprise adding the initiator to the solvent before, after, or during any one or more of the dissolving of the monomer in the solvent.

Chain transfer agents are used to limit the molecular weight of the copolymer to within the desired range. Any suitable chain transfer agent may be used. For example, the chain transfer agent may include any one or more mercaptans, such as octyl mercaptan, hexyl mercaptan, 2-mercaptoethanol, n-dodecyl mercaptan, and t-dodecyl mercaptan. When used, the chain transfer agent may be used, for example, in an amount of at least about 1 weight percent or at least about 2 weight percent, and up to about 10 weight percent, up to about 7 weight percent, or up to about 5 weight percent, based on the combined weight of the monomers to be copolymerized. Likewise, any suitable initiator can be used in the process of making the disclosed pigment dispersion resins. For example, the initiator may comprise any one or more azo compounds, such as 2,2 '-azobis (2-methylpropionitrile) and 2,2' -azobis (2-methylbutyronitrile); hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide; peracetate esters such as tert-butyl peracetate; peroxides such as benzoyl peroxide, di-t-butyl peroxide and methyl ethyl ketone peroxide; peroxy esters, such as tert-butyl perbenzoate and tert-amyl perbenzoate; percarbonates, such as isopropyl percarbonate; peroctoates, such as tert-butyl peroctoate; and peroxycarbonates, such as butyl isopropyl peroxycarbonate. When used, the initiator may be used, for example, in an amount of at least about 1 weight percent or at least about 3 weight percent, and up to about 15 weight percent or up to about 7 weight percent, based on the combined weight of the monomers to be copolymerized.

The disclosed resins can be prepared by any suitable technique. For example, the resin may be prepared by an addition polymerization reaction using a PM Acetate solvent, isobornyl (meth) acrylate monomer, methyl (meth) acrylate monomer, n-dodecyl mercaptan chain transfer agent, and tert-butyl peroctoate initiator using the following sequence of steps. One of ordinary skill in the art will appreciate that conventional techniques should be used to select and monitor suitable reaction times and temperatures for conducting the reaction in the selected reactor vessel or other equipment:

1. the solvent is added to the reactor and heated to the appropriate temperature.

2. Isobornyl (meth) acrylate monomer, methyl (meth) acrylate monomer, and n-dodecyl mercaptan chain transfer agent are mixed in a feed tank and fed to the reaction vessel at a selected temperature for a selected period of time.

3. Simultaneously with step 2, the solvent and t-butyl peroctoate initiator are mixed together in an initiator tank and fed into the reaction vessel at a selected temperature for a selected period of time.

4. The batch is then maintained at the reaction temperature and then the temperature is reduced after a suitable time has elapsed to allow the batch to cool to a suitably lower temperature.

5. T-butyl peroctoate co-promoter (boost) was added and held at a lower temperature for an appropriate time.

6. The booster is added and again held at a lower temperature for an appropriate time.

7. After holding, the copolymer product is cooled and solvent is added to achieve the desired solids content.

When used as a pigment dispersion resin, the disclosed copolymers can be provided as a solution in one or more solvents. The solvent may conveniently be the same as that used to prepare the copolymer. In some embodiments, additional or different solvents may be used. Can be used in combination with the colorAny one or more known solvents are used with the dispersion resin, including polar and non-polar solvents. Such solvents can be different from or the same as the solvents used to form the disclosed pigment vehicles or the disclosed coating compositions. For example, the PM Acetate may be a solvent contained in the pigment dispersion resin or the pigment vehicle. Other suitable solvents include ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, and methyl isobutyl ketone; glycol ethers, such as propylene glycol ether and ethylene glycol ether, preferably ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monopropyl ether; acetates, such as glycol ether acetates, preferably PM Acetate; aromatic hydrocarbons such as toluene, naphthalene and xylene; for special solvents that are compliant in California and other jurisdictions, e.g. Oxsol^TM100 p-chlorotrifluoromethylene (from islecem) and tert-butyl acetate; aliphatic hydrocarbons such as pentane, hexane and heptane; petroleum and wood distillates; turpentine oil; pine oil; mineral oleins, such as odorless mineral olein and low flash grade, normal grade or high flash grade mineral olein of type 0, type 1, type 2, type 3, and the like. Exemplary pigment dispersion resins comprise greater than about 20 wt%, greater than about 30 wt%, greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, or greater than about 80 wt% solids or non-volatile materials. In some embodiments, the disclosed pigment dispersion resins may comprise from about 40% to about 70%, or from about 50% to about 60%, by weight, solids or non-volatile materials.

The disclosed pigment dispersion resins are particularly useful in preparing pigment vehicles comprising the resins and a plurality of pigment particles. Without being bound by theory, it is believed that the generally polar (e.g., hydrophilic portion) of the monomer units in the pigment dispersion resin facilitates formulation of a pigment vehicle having a high concentration of pigment particles, while still allowing the pigment vehicle to have properties approaching those of a newtonian fluid.

The disclosed pigment vehicles may comprise any of a number of suitable pigment particles and pigment extenders, such as azo pigments, chalcopyrite (azurite), aluminum silicate, potassium aluminum silicate, aluminum paste, anthraquinone pigments, antimony oxide, barium metaborate, barium sulfate, cadmium sulfide, cadmium selenide, calcium carbonate, calcium metaborate, calcium metasilicate, carbon black, chromium oxide, clays, copper oxide, copper oxychloride, dioxazine pigments, feldspar, hansa yellow azo pigments, some of which are listed above, benzimidazolone, iron oxides (e.g., yellow and red iron oxides), isoindoline pigments, kaolinite, lithopone, magnesium silicate, metal flakes, mica, naphthol pigments (e.g., naphthol red), nitroso pigments, nepheline syenite, pyreneone pigments, perylene pigments, polycyclic pigments, pyrrolopyrrole pigments, phthalocyanines such as copper phthalocyanine blue and copper phthalocyanine green, Quinacridones (such as quinacridone violet), quinophthalone pigments, silicates, sulfides, talc, titanium dioxide, ultramarine blue, zinc chromate, zinc oxide and zinc phosphate. Exemplary pigment vehicles can, for example, include a pigment and a pigment dispersion resin in a pigment to pigment dispersion resin weight ratio of about 0.1 to about 7, about 0.5 to about 6.0, or about 0.75 to about 5.0.

The disclosed pigment vehicles may also contain a variety of other ingredients, including any one or more pearlescent agents, optical brighteners, ultraviolet light stabilizers, conventional dispersants, surfactants, wetting agents, synergists, and rheology modifiers. These materials are preferably dispersible or soluble in a wide range of solvents from non-polar solvents (e.g. odorless mineral spirits) to polar solvents (e.g. methyl ethyl ketone). Exemplary conventional dispersants include any one or more of anionic, cationic, amphoteric or nonionic dispersants useful in conventional pigment vehicles, including various block copolymers, polyester and acrylic dispersants specifically used in solvent borne pigment dispersions. Examples of such conventional dispersants include NUOSPERSE available from elementis specialties^TM657 and NUOSPERSE FA 196 DISPERBYK available from Altana AG^TM108 and SOLSPERSETM M387 available from Lubrizol Corporation. Exemplary wetting agents include any one or more anionic, cationic, amphoteric or nonionic wetting agents that can be used in conventional pigment vehicles. Exemplary synergists include those suitable for use in conventional pigment vehicles, such as SOLSPERSE 50 available from Lubrizol corporation00. Exemplary rheology modifiers include any one or more rheology modifiers that can be used in conventional pigment vehicles, such as suspano available from Poly-Resyn, inc^TM201-MS and AEROSIL available from Evonik Industries^TM. The disclosed pigment vehicles can be prepared from the disclosed pigment dispersion resins and selected pigments by various mixing techniques familiar to those of ordinary skill in the art.

An exemplary iron oxide red pigment vehicle can, for example, include about 15% to about 22% by weight of the disclosed pigment dispersion resin, about 7% to about 12% by weight of PM Acetate, about 1% to about 4% by weight of SOLSPERSE M387 conventional dispersant, and about 65 to about 75% by weight of iron oxide red. An exemplary black pigment vehicle may, for example, include from about 34 to about 44 weight percent of the disclosed pigment dispersion resin, from about 24 to about 34 weight percent of PMAcetate, from about 0.5 to about 1.5 weight percent of NUOSPERSE FA 196 conventional dispersant, from 2.5 to about 3.5 weight percent of SOLSPERSE M387 conventional dispersant, and from about 24 to about 34 weight percent of carbon black. An exemplary blue pigment vehicle may, for example, include from about 27% to about 37% by weight of the disclosed pigment dispersion resin, from about 25% to about 35% by weight of PMAcetate, from about 0.5% to about 1.5% by weight of NUOSPERSE FA 196 conventional dispersant, from 4 to about 8% by weight of SOLSPERSE M387 conventional dispersant, and from 26 to about 36% by weight of phthalocyanine blue pigment (PB 15: 2).

The disclosed pigment vehicles can be used to prepare a variety of coating compositions. Generally, a method for preparing a coating composition includes mixing a carrier liquid, a binder resin, and a pigment vehicle, wherein the pigment vehicle comprises a plurality of pigment particles and the disclosed pigment dispersion resin. The coating composition may generally be a paint, although it is contemplated in some embodiments that the techniques disclosed herein may be used with other types of coating compositions, such as stains. In one embodiment, the disclosed method includes using a single such pigment vehicle to produce a plurality of coating compositions, including at least one coating composition comprising a film-forming binder resin and a polar non-aqueous solvent and at least one coating composition comprising a film-forming binder resin and a non-polar solvent.

The carrier liquid is the fluid component of the coating composition, which serves to carry all other components of the composition and evaporates as the composition dries. A variety of suitable carrier liquids can be used, including any one or more polar or non-polar solvents, including the above-mentioned solvents that can be used to make the disclosed pigment dispersion resins or the disclosed pigment vehicles.

In some embodiments, the binder resin preferably comprises any one or more of vinyl, acrylic, modified acrylic, vinyl acrylic alkyd, styrene acrylic alkyd, epoxy ester, long oil alkyd, short oil alkyd, medium oil alkyd, coconut alkyd, phenolic modified alkyd, nitrocellulose, CAB, polyester, polyurethane or epoxy resins the binder resin may be non-crosslinkable, crosslinkable or crosslinked the acrylic polymer is a particularly useful binder resin exemplary acrylic polymers are formed from monomers comprising at least one acrylic monomer, for example, from at least one acrylic monomer and a vinyl aromatic hydrocarbon (e.g., styrene, methyl styrene or other lower alkyl styrene, chlorostyrene, vinyl toluene, vinyl naphthalene or divinyl benzene) suitable acrylic monomers include various compounds having an acrylic functional group, such as (meth) acrylic acid alkyl esters, (meth) acrylic acid esters such as benzyl methacrylate, (meth) acrylic acid, glycidyl (meth) acrylate, glycidyl methacrylate, acrylic acid (meth) acrylate, glycidyl methacrylate, acrylic acid (meth) acrylate, methacrylate, glycidyl methacrylate.

In some embodiments of the disclosed methods for making a coating composition, the binder resin may comprise one or more polyesters (e.g., alkyds) or epoxy binder resins. Alkyd resins and other polyesters may be prepared in known manner by condensation of polyols and polycarboxylic acids, with or without the inclusion of natural drying oil fatty acids. The polyester may contain a proportion of free hydroxyl or carboxyl groups which may be used to react with a suitable cross-linking agent if desired. The epoxy resin typically comprises an epoxy resin in combination with one or more of an aliphatic or aromatic amine curing agent, a polyamide curing agent, or a thiol-based curing agent. Exemplary epoxy resins include those formed from bisphenol a or bisphenol F, while suitable amine curing agents include aliphatic amines, phenolic amines (phenalkamines), cycloaliphatic amines, amidoamines, and polyamides. It is contemplated that alkyd resins will typically be used with mineral spirits as the carrier liquid.

Additives can be added at any suitable point during the manufacture of the disclosed coating compositions. Exemplary additives include any one or more of neutralizing agents, defoamers, fillers, dyes, dispersants, surfactants, extenders, tackifiers, wetting agents, rheology modifiers, leveling agents, antiblocking agents, mildewcides, fungicides, algaecides, bactericides, other preservatives, thickeners, thixotropic agents, drying agents, anti-settling agents, and leveling agents. When used, such additives may be present in any amount suitable for their intended purpose. It is expected that some additives will play multiple roles in the disclosed coating compositions.

Generally, the process for making the disclosed coating compositions can include three or more stages, including an optional pre-dilution stage (which can typically be omitted when preparing the colorant), a milling stage, a washing stage, and a thinning stage. In the pre-dilution stage, one or more binder resins may be mixed with a liquid in a dilution tank (thindown tank), and low shear mixing may be performed in the dilution tank to form a pre-diluted mixture. The liquid added in the pre-dilution stage can include any one or more of the solvents described herein in connection with the pigment dispersion resin. In the milling stage, a plurality of pigment particles and the disclosed pigment dispersion resin can be mixed in a high shear mixing device, such as a mill, to produce a mill paste. The high shear forces applied during the milling stage are intended to break up agglomerates of the pigment particles and ensure wetting of the particles by the resin. A carrier liquid comprising any one or more of the carrier liquids described herein may also be added during the milling stage. In the washing stage, a wash liquid comprising any one or more of the solvents described herein in connection with the pigment dispersion resin may be pumped into the high shear mixing device to move the mill paste into the dilution tank. In the thinning stage, the abrasive paste, carrier liquid and washing liquid are blended together in a thinning tank under low shear conditions. These components may also be blended together with the pre-diluted mixture in a dilution tank. The coating composition concentrate may be further diluted by further adding a liquid comprising any one or more of the solvents described herein. The disclosed method of making the coating composition may employ these conventional steps, or may employ other suitable methods, such as continuous manufacturing using a slurry of the components.

Once prepared, the disclosed coating compositions can be dispensed into a storage container such as a tank or drum. When the storage container is opened, the coating composition may be applied to a substrate, such as wood, drywall (drywall), metal, plastic, or composite materials. The composition may be applied using any means suitable for applying the coating composition, such as a brush, roller, sponge or spray gun. Upon application, the liquid in the composition will evaporate and the binder resin of the coating composition will form a film which, upon drying or curing, will yield the desired coating.

The following examples are provided to illustrate the invention, but should not be construed as limiting its scope.

Examples