WO2016101094A1

WO2016101094A1 - Use of an alkoxylated compound for reducing combining of coating particles on a substrate and the method thereof

Info

Publication number: WO2016101094A1
Application number: PCT/CN2014/094495
Authority: WO
Inventors: Jing Qiu LI; Yan Hui CHEN; Peng Xu
Original assignee: Rhodia Operations
Priority date: 2014-12-22
Filing date: 2014-12-22
Publication date: 2016-06-30
Also published as: CN107108454A

Abstract

The present invention provides the use of a particular family of alkoxylated compounds, e.g. alkoxylatedalkyldistyrylphenol, alkoxylatedtristyrylphenol and alkoxylatedtributylphenol, in a coating composition for reducing combining of coating particles on a substrate and the methods thereof. The alkoxylated compounds may be incorporated into a latex polymer or post added to an already formed coating composition. The substrate may be a coating applying apparatus, as well as an article or a material which is subject to coatings or paints.

Description

Use of an alkoxylated compound for reducing combining of coating particles on a substrate and the method thereof

Technical Field

The present invention relates to the use of a particular family of alkoxylated compounds, e.g. alkoxylatedalkyldistyrylphenol, alkoxylatedtristyrylphenol and alkoxylatedtributylphenol, in a coating composition for reducing combining of coating particles on a substrate. In particular, the present invention relates to the use of certain reactive polymerizablealkoxylated compound based monomers, surface active alkoxylated compound surfactants, and surface active alkoxylated compound additives for reducing combining of coating particles that are contained in an aqueous latex dispersion, an aqueous latex binder and an aqueous coating on a substrate.

Background Art

In the paint and coating industry, traditional solvent-borne paints and coatings are being replaced with waterborne system due to concerns regarding the impact of Volatile Organic Compounds (VOC) to human health and the environment. In addition, recently enacted environmental legislation requires the reduction of the amount of Volatile Organic Compounds (VOC) in coatings. For example, SCAQMD (South Coast Air Quality Management District) in California and OTC (Ozone Transport Commission) in the East Coast states, have required reduced amounts of VOC emissions of coatings & paints products, especially architectural and industrial paints and coatings (after application of a coating to a substrate, VOCs slowly evaporate into the surroundings) .

These regulations are forcing polymers and paints manufactures to develop lower VOC products. However, the waterborne technologies for lower or zero VOC paints and coatings have many challenges and drawbacks especially in achieving the key performances compared to solvent-based coatings or high VOC paint products.

Paints or coatings are usually applied to a surface to be painted or coated by using a coating applying apparatus, such as a brush or a roller. One problem associated with waterborne coatings and paints is that coating particles that are contained in the paints or the coatings tend to form coagulation on the coating applying apparatus. For example, in the case wherein a brush or a roller is used, when the brush or the roller is immersed in a paint or a coating for a certain period, the coating particles may form coagulation or clot on the brush hair or the surface of the roller, leading to the hardening of the brush hair or the surface of the roller. In particular, such coagulation of the coating particles will occur on brushes or rollers made of nature fibers (such as wool) which are subject to acidic treatment during manufacture for removing the fats in the natural fibers. When this happens, the brush or the roller cannot be used anymore or need to be substantially washed to remove the coagulation or the clot before being used again for painting or coating. To mitigate the hardening of the brush or the roller, one may reduce the immersing time of the brush or the roller in the paint or the coating. Even by doing this, significant amount of grits (aggregation of the coating particles) can still be found on a paint film in consequence. In addition, when the coating or the paint is applied to a surface which contains an acidic material, the coating particles may also form coagulation on the surface being coated/painted, thus affecting the quality of the coating/painting.

There is a need to provide a paint composition or a coating composition which does not form coagulation on a paint applying apparatus or a surface to be coated/painted.

Summary of invention

In a first aspect of the present invention, there is provided use of a compound having the general formula of IA in a coating composition for reducing combining of coating particles on a substrate :

wherein B is a 5 or 6 membered cycloalkyl ring or a single ring aromatic hydrocarbon having a 6 membered ring；

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein X is C₂H₄, C₃H₆, or C₄H_8, or X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is an integer of from 1 to 100；

wherein R is selected from an ethylenically unsaturated group, -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H_11, -OC₆H_13, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation.

In one embodiment, the compound has the general formula of IB :

wherein R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

n is an integer of from 1 to 100；

In a second aspect of the present invention, there is provided a use of a monomer (second monomer) having the general formula of IIA for reducing combining of coating particles on a substrate wherein the second monomer is copolymerized with at least one first monomer into the backbone of a latex polymer used for forming a coating composition:

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is C₂H₄, C₃H₆, or C₄H_8, or X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is an integer of from 1 to 100；

wherein R is an ethylenically unsaturated group.

In one embodiment, the second monomer has the general formula of IIB :

wherein R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

n is an integer of from 1 to 100；

R is an ethylenically unsaturated group.

In another embodiment, the second monomer has the general formula of IIC or IIC-1

wherein n is an integer of from 1-100；

R₄ is a member of the group consisting of H, C₁-C₈hydroxy alkyl, C₁-C₆ alkyl.

In a third aspect of the present invention, there is provided a use of an additive in a coating composition for reducing combining of coating particles on a substrate wherein the additive comprises at least one compound having the general formula of IIIA :

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H, tertbutyl, butyl,

with the proviso that one or none of R₁, R₂ and R₃ is –H；

wherein X is at least one member of the group consisting of C₂H₄, C₃H₆, and C₄H₈, or wherein X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is 1-100, for example, 3 to 80, 4 to 60, 4 to 60 or 8 to 50；

wherein R is -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H_11, -OC₆H_13, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a nonionic group, a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation including but not limited to H⁺, Na⁺, NH₄ ⁺, K⁺, Li⁺ or –N (R₁₁) ₄ ⁺wherein R₁₁ is a –H or a C₁-C₆ alkyl group and at least one R₁₁ is a C₁-C₆ alkyl group.

In one embodiment, the compound has the general formula of IIIB :

wherein R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is at least one member of the group consisting of C₂H₄, C₃H₆, and C₄H₈, or wherein X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is 1-100；

wherein R is -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H_11, -OC₆H_13, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation.

In one embodiment, the compound has the general formula of IIIC or IIIC1 :

wherein n is an integer of from 1 to 100；

R₅ is -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H_11, -OC₆H_13, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation.

In one embodiment, the cation may be H⁺, Na⁺, NH₄ ⁺, K⁺, Li⁺ or–N(R₁₁) ₄ ⁺wherein R₁₁ is a –H or a C₁-C₆ alkyl group and at least one R₁₁ is a C₁-C₆ alkyl group.

In one embodiment, the additive is a blend of

(i) at least one non-ionic surfactant having formula:

wherein, n is an integer of from 1 to 100；

R₅ is selected from the group consisting of a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -Cl, -Br, -CN, -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H_9, -OC₅H_11, and-OC₆H₁₃； and

(ii) at least one anionic surfactant having formula:

wherein, n is an integer of from 1 to 100；

R₅ is selected from the group consisting of alkylphosphonate, alkylphosphate, alkylsulfate, alkylsulfonate, phosphonate, phosphate, sulfate, sulfonate, carboxylate and any salt thereof.

In a fourth aspect of the present invention, there is provided a method for reducing combining of coating particles on a substrate by including in a coating composition a compound having the general formula of IA :

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

n is an integer of from 1 to 100；

In a fifth aspect of the present invention, there is provided a method for reducing combining of coating particles on a substrate comprising the step of copolymerizing a monomer (second monomer) having the general formula of IIA with at least one first monomer into the backbone of a latex polymer used for forming a coating composition:

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is C₂H₄, C₃H₆, or C₄H_8, or X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms； n is an integer of from 1 to 100；

wherein R is an ethylenically unsaturated group.

In a sixth aspect of the present invention, there is provided a method for reducing combining of coating particles on a substrate comprising the step of adding in a coating composition an additive comprising at least one compound having the general formula of IIIA :

wherein B is a 5 or 6 membered cycloalkyl ring；

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

n is 1-100；

According to the present invention, the substrate may be a coating applying apparatus.

According to the present invention, the substrate may be a coating applying apparatus which is subject to acidic treatment prior to coming into contact with the coating composition.

Detailed Description

The present invention relates to the use of a particular family of alkoxylated compounds, e.g., alkoxylatedalkyldistyrylphenol, alkoxylatedtristyrylphenols and alkoxylatedtributylphenols, for reducing combining of coating particles on a substrate. This family of alkoxylated compounds can reduce or prevent the combining of the coating particles that are contained in the coating composition on the substrate. Typically, the coating composition is an aqueous coating composition.

The present invention also relates to a method for reducing combining of coating particles on a substrate by including the alkoxylated compounds in a coating composition.

As used herein, the term “coating composition” includes and is not limited to latex binders, resins, glues, adhesives which include and are not limited to pressure sensitive adhesives, inks which include and are not limited to UV inks, conventional inks, hybrid inks, and water-based inks, sealants, cement compositions, coatings which include and are not limited to paints.

As used herein, the term "alkyl" means a saturated hydrocarbon radical, which may be straight, branched or cyclic, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl.

As used herein, the term "cycloalkyl"means a saturated hydrocarbon radical that includes one or more cyclic alkyl rings, for example, cyclopentyl, cyclooctyl, and adamantanyl.

As used herein, the term "hydroxyalkyl"means an alkyl radical, more typically an alkyl radical, that is substituted with a hydroxyl groups, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxydecyl.

As used herein, the term "alkylene" means a bivalent acyclic saturated hydrocarbon radical, including but not limited to methylene, polymethylene, and alkyl substituted polymethylene radicals, for example, dimethylene, tetramethylene, and 2-methyltrimethylene.

As used herein, the term "alkenyl" means an unsaturated straight chain, branched chain, or cyclic hydrocarbon radical that contains one or more carbon-carbon double bonds, for example, ethenyl, 1-propenyl, 2-propenyl.

As used herein, the term "aryl" means a monovalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds, which may be substituted one or more of carbons of the ring with hydroxy, alkyl, alkenyl, halo, haloalkyl, or amino, for example, phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl.

As used herein, the term "aralkyl" means an alkyl group substituted with one or more aryl groups, for example, phenylmethyl, phenylethyl, triphenylmethyl.

As used herein, the terminology " (C_n-C_m) " in reference to an organic group, wherein n and m are each integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.

As used herein, the terminology “ethylenic unsaturation” means a terminal (that is, e.g., α, β) carbon-carbon double bond.

As used herein, the term “coating particles” means solid, semisolid or liquid particles dispersed in a suspension of a coating composition (i.e., the suspension may be a dispersion or an emulsion) . In the context of the present application, the coating particles include and are not limited to binder particles, pigment particles, filler particles.

As used herein, the term “combining of coating particles” means the phenomenon that coating particles that are contained in a coating composition combine irreversibly. That is the combined coating particles will not return to their uncombined (i.e., separated or dispersed) condition naturally over time. The process by which the coating particles combine may be described generally as one or more of the following : aggregation, coalescence, agglomeration, flocculation, coagulation and/or precipitation.

As used herein, the term “coating applying apparatus” means an apparatus which can be used for applying paints or coatings to a surface, including but not being limited to a brush, a roller, a mop and the like.

As used herein, the term “substrate” means a coating applying apparatus, as well as an article or a material which is subject to coatings or paints, such as paper, wood, concrete, metal, glass, ceramics, plastics, plaster, an asphaltic coating, a roofing felt, foamed polyurethane insulation, or a previously painted, primed, undercoated, worn, or weathered article.

Generally, to maintain the stability of a coating composition, the coating composition is preferably maintained under alkaline condition. For example, the pH value of the coating composition is usually maintained in the region of 7 to 10. Under such condition, coating particles that are contained in the coating composition will remain evenly distributed. However, when the coating composition comes into contact with a substrate, a fluctuation of the pH value, such as a decrease in the pH value, may occur on the surface of the substrate or in a region within the coating composition which is adjacent to the surface of the substrate even with the presence of one or more neutralizers in the coating composition. This may lead to the combining of the coating particles on the substrate. As a result, the coating particles may form aggregation, coalescence, agglomeration, flocculation, coagulation and/or precipitation on the substrate. In particular, such combining of the coating particles on the substrate may be apparent wherein the substrate has been subject to acidic treatment prior to coming into contact with the coating composition or wherein the substrate contains an acidic material. While not wishing to be bound by theory, it is believed that surfaces of the coating particles in the coating composition, such as latex particles, pigment particles or filler particles, are negatively charged under storage or stand-by conditions. When the coating composition comes into contact with the substrate wherein the fluctuation of the pH value occurs, the surfaces of the coating particles may become re-protoated or positively charged, leading to the combining of the coating particles on the substrate. Surprisingly, it has been found that, in accordance with the present invention, the alkoxylated compounds of the present invention could function to reduce or prevent the combining of the coating particles on the substrate, thus, the coating composition comprising the alkoxylated compounds could have reduced coagulation on the substrate.

In one aspect of the present invention, the alkoxylated compounds have the general formula of

wherein B is a 5 or 6 membered cycloalkyl ring, e.g., a cyclohexyl ring, or a single ring aromatic hydrocarbon having a 6 membered ring, e.g., a benzene ring；

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl (e.g., butyl, tert-butyl and isobutyl) , hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

n is an integer of from 1 to 100,

wherein R is selected from an ethylenically unsaturated group, -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H_11, -OC₆H_13, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation including but not limited to H⁺, Na⁺, NH₄ ⁺, K⁺, Li⁺ or–N (R₁₁) ₄ ⁺wherein R₁₁ is a –H or a C₁-C₆ alkyl group and at least one R₁₁ is a C₁-C₆ alkyl group.

In one embodiment, the alkoxylated compounds have the general formula of

wherein, R, R₁, R₂, R₃, X and n are as defined for the structure of formula IA. If desired, the aromatic ring shown in formula IB may be saturated. For example, such a saturated monomer may be made by saturating a form of the monomer wherein H is in the R position and then replacing the H in the R position with one of the other above-listed R groups.

The alkoxylated compounds of the present invention, e.g., alkoxylatedalkyldistyrylphenol , alkoxylatedtristyrylphenols and/or tributylphenols, can be employed in a number of ways for reducing combining of the coating particles on the substrate. The present invention may employ one or any combination of (i) employing a reactive polymerizablealkoxylated monomer as a reactant during emulsion polymerization to form a latex polymer, (ii) employing one or more surface active alkoxylated compounds described herein as a surfactant (emulsifier) during emulsion polymerization to form a latex polymer, and/or (iii) employing a surface active alkoxylated compound as an additive to a coating composition, in particular an aqueous coating composition which includes but is not limited to a paint, as well as an additive to an adhesive, a glue, a resin, a sealant, an ink and the like. The resulting coating composition containing the alkoxylated compounds of the present invention can have reduced coagulation on the substrate.

Reactive polymerizabletristyrylphenolethoxylates

In one aspect, the present invention provides the use of a reactive polymerizablealkoxylated monomer for reducing combining of coating particles on a substrate wherein the reactive polymerizablealkoxylated (second) monomer of the following formula IIA can be copolymerized with at least one first monomer into the backbone of a latex polymer used for forming a coating composition :

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl (e.g., butyl, tert-butyl, isobutyl) , hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

n is an integer of from 1 to 100, for example from about 4 to 80 or 8 to 60；

wherein R is an ethylenically unsaturated group.

In one embodiment, n is an integer of from 4 to 80. In another embodiment, n is an integer of from 4 to 60. In still another embodiment, n is an integer of from 10 to 60. In still another embodiment, n is an integer of from 10 to 50.

Typically, R includes acrylate, or C₁-C₆ alkyl acrylate, e.g., methacrylate, allyl, vinyl, maleate, itaconate or fumarate, typically R is acrylate or methacrylate.

Suitable polymerizable functional groups R include, for example, acrylo, methacrylo, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α-alkenyl, maleimido, styrenyl, and α-alkyl styrenyl groups.

For example, suitable polymerizable functional groups R have the chemical structure: R^aCH＝C (R^b) COO-, wherein if R^a is H, then R^b is H, C₁-C₄ alkyl, or -CH₂COOX； if R^a is –C (O) OX, then R^b is H or –CH₂C (O) OX^a； or if R^a is CH₃, then R^b is H and X^a is H or C₁-C₄ alkyl.

For example, other suitable polymerizable functional groups R have the chemical structure: -HC＝CYZ or -OCH＝CYZ, wherein Y is H, CH₃, or Cl ；

Z is CN, Cl, -COOR^c, -C₆H₄R^c, -COOR^d, or -HC＝CH₂； R^d is C₁ –C₈ alkyl or C₂–C₈ hydroxy alkyl； R^c is H, Cl, Br, or C₁-C₄ alkyl.

Typically the reactive polymerizablealkoxylated monomer has the formula of IIB:

wherein, R, R₁, R₂, R₃, X and n are as defined for the structure of formula IIA. If desired, the aromatic ring shown in structural formula IIB may be saturated. For example, such a saturated monomer may be made by saturating a form of the monomer wherein H is in the R position and then replacing the H in the R position with one of the other above-listed R groups.

In one embodiment, at least one of R₁, R₂ and R₃ is a C₁-C₁₈ alkyl and the rest of R₁, R₂ and R₃ are

. Preferably, at least one of R₁, R₂ and R₃ is a C₄-C₁₈ alkyl and the rest of R₁, R₂ and R₃ are

. For example, the compound of the formula IIB may be an alkoxylatedalkyldistyrylphenol.

In another embodiment, at least one monomer can be copolymerized with a second monomer having the formula IIB-1:

wherein R is

R₁, R₂ and R₃ are each independently H, branched (C₃-C₈ alkyl) , branched (C₄-C₈) alkene or R₅-R₆-；

R₅ is aryl or (C₆-C₈) cycloalkyl,

R₆ is (C₁-C₆) alkylene,

R7 is a divalent linking group, such as –O-, (C₁-C₆) alkylene and

, R₇ is optional；

R₈ is H or methyl；

R₉ is –O- or NR_10；

R₁₀ is H or (C₁-C₄) alkyl；

n is an integer of from 2 to 4, and m is an integer of from 1 to 100.

In one embodiment, R₁, R₂ and R₃ are independently selected from:

In one embodiment, R can be acrylate, C₁-C₆ alkyl acrylate, allyl, vinyl, maleate, itaconate or fumarate. In one embodiment, R is at least one of acrylo, methacrylo, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α-alkenyl, maleimido, styrenyl, and/or α-alkyl styrenyl groups.

In another embodiment, the reactive polymerizablealkoxylated monomer is an ethoxylatedtributylphenol. In another embodiment, the reactive polymerizablealkoxylated monomer is an ethoxylatedtristyrylphenol. The reactive polymerizableethoxylatedtristyrylphenols have the structural formula IIC and the reactive polymerizableethoxylatedtributylphenols have the structural formula IIC-1, respectively, as follows:

wherein, n is an integer of from 1-100, for example, 4 to 80 or 8 to 25；

R₄ is a member of the group H, C₁-C₈hydroxy alkyl, C₁-C₆ alkyl, for example, CH₃ or C₂H₅.

Thus, the reactive polymerizableethoxylatedtristyrylphenol monomer has a tristyrylphenol portion, an alkylene oxide portion and a reactive substituted or unsubstituted acrylic end group for polymerization. Likewise, the reactive polymerizableethoxylatedtributylphenol monomer has a tributylphenol portion, an alkylene oxide portion and a reactive substituted or unsubstituted acrylic end group for polymerization. If desired, the ethylene oxide group shown in structural formula IIC or IIC-1 may be replaced with the above discussed - (OX) -group to form an alkoxylatedtristyrylphenol or tributylphenol, respectively, and the -C (O) -CHR₄CH₂ end group may be replaced by allyl, vinyl, maleate, itaconate or fumarate.

If desired the aromatic rings of the styryl groups in Formula IIC may be saturated.

In another aspect, the present invention provides a method for reducing combining of coating particles on a substrate comprising the step of copolymerizing a reactive polymerizablealkoxylated (second) monomer having the general formula of IIA, IIB, IIC and/or IIC-1 as described above with at least one first monomer into the backbone of a latex polymer.

When the reactive polymerizablealkoxylated monomer of IIA, IIB, IIC and/or IIC-1 is copolymerized into the backbone of the latex polymer, the latex polymer is made from a mixture wherein the reactive polymerizablealkoxylated monomer is 1 to 20 parts per 100 parts by weight of monomers used to form the copolymer, more typically 2 to 15, 2 to 8, or 2 to 6 parts per 100 parts by weight of monomers used to form the copolymer. In one embodiment, both the reactive polymerizablealkoxylated monomer of formula IIC and IIC-1 are utilized and copolymerized into the backbone of the latex polymer.

Other Monomers

In addition to the reactive polymerizablealkoxylated monomer as described above, there are other monomers from which at least one latex polymer used in the aqueous coating composition, e.g., paint, is typically derived. For purposes of this description, these other monomers from which the latex polymers may be derived are termed latex monomers. Typically, these other latex monomers comprise at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters. In addition, the other monomers for making the latex polymer can optionally be selected from one or more monomers selected from the group consisting of styrene, a-methyl styrene, vinyl chloride, acrylonitrile, methacrylonitrile, ureido methacrylate, vinyl acetate, vinyl esters of branched tertiary monocarboxylic acids (e.g. vinyl esters commercially available under the mark VEOVA from Shell Chemical Company or sold as EXXAR Neo Vinyl Esters by ExxonMobil Chemical Company) , itaconic acid, crotonic acid, maleic acid, fumaric acid, and ethylene. It is also possible to include C₄-C₈ conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene. Typically, the monomers include one or more monomers selected from the group consisting of n-butyl acrylate, methyl methacrylate, styrene and 2-ethylhexyl acrylate. The latex polymer is typically selected from the group consisting of pure acrylics (comprising acrylic acid, methacrylic acid, an acrylate ester, and/or a methacrylate ester as the main monomers) ；styrene acrylics (comprising styrene and acrylic acid, methacrylic acid, an acrylate ester, and/or a methacrylate ester as the main monomers) ； vinyl acrylics (comprising vinyl acetate and acrylic acid, methacrylic acid, an acrylate ester, and/or a methacrylate ester as the main monomers) ； and acrylated ethylene vinyl acetate copolymers (comprising ethylene, vinyl acetate and acrylic acid, methacrylic acid, an acrylate ester, and/or a methacrylate ester as the main monomers) . The monomers can also include other main monomers such as acrylamide and acrylonitrile, and one or more functional monomers such as itaconic acid and ureido methacrylate, as would be readily understood by those skilled in the art. In a particularly preferred embodiment, the latex polymer is a pure acrylic such as a butyl acrylate/methyl methacrylate copolymer derived from monomers including butyl acrylate and methyl methacrylate.

In one embodiment, the reactive polymerizablealkoxylated monomer of formula IIA, IIB, IIC and/or IIC-1 are utilized and copolymerized with one of the monomers listed under “other monomers” into the backbone of a latex polymer under reaction conditions. In another embodiment, the reactive polymerizablealkoxylated monomer of formula IIA, IIB, IIC and/or IIC-1 are utilized and copolymerized with two or more of the monomers listed under “other monomers” into the backbone of a latex polymer under reaction conditions. In another embodiment, one or more reactive polymerizablealkoxylated monomers of formula IIA, IIB, IIC and/or IIC-1 are utilized and copolymerized with one or more of the monomers listed under “other monomers” into the backbone of a latex polymer under reaction conditions.

The latex polymer dispersion typically includes from about 30 to about 75％solids and a mean latex particle size of from about 70 to about 650 nm. In another embodiment, the polymer of the present invention has a mean particle size of less than about 400nm, typically a mean particle size of less than about 200 nm, more typically a mean particle size of less than about 190 nm, and most typically a mean particle size of less than about 175 nm. In another embodiment, the polymer has a mean particle size of from about 75 nm to about 400 nm.

The latex polymer is typically present in the coating composition in an amount from about 5 to about 60 percent by weight, and more typically from about 8 to about 40 percent by weight (i.e. the weight percentage of the dry latex polymer based on the total weight of the coating composition) . Typically, the coating composition is an aqueous coating composition.

In another embodiment, the resulting latex polymer may be incorporated into the coating composition (such as the aqueous coating composition) along with the coagulation reducing additive described below. The addition of the coagulation reducing additive has little or no effect on the VOC levels of the aqueous coating composition, and, thus, aqueous coating compositions which possess lower VOC levels than conventional aqueous coating compositions can be produced. In such an embodiment, the coating composition contains the coagulation reducing additive as described herein in an amount greater than about 1.3％by weight of the polymer. In another embodiment, the coating composition contains the coagulation reducing additive as described herein in an amount greater than about 1.6％by weight of the polymer. In another embodiment, the coating composition contains the coagulation reducing additive as described herein in an amount greater than about 2％by weight of the polymer. In another embodiment, the coating composition contains the coagulation reducing additive as described herein in an amount greater than about 4％by weight of the polymer. In another embodiment, the coating composition contains the coagulation reducing additive as described herein in an amount greater than about 7.5％by weight of the polymer. In another embodiment, the coating composition contains the coagulation reducing additive as described herein in an amount greater than about 8％by weight of the polymer. In another embodiment, the coating composition contains the coagulation reducing additive in an amount between about 1.6％and 7.5％by weight of the polymer. In another embodiment, the coating composition contains the coagulation reducing additive in an amount between about 1.6％and 45％by weight of the polymer, typically between about 1.6％and 35％by weight of the polymer.

The latex polymer including the reactive polymerizablealkoxylated monomer of formula IIA, IIB or IIC can be used in combination with other ionic or non-ionic type of surfactants that are either polymerizable or non-polymerizable in the coating composition. In particular, the polymer latex binder can be prepared using emulsion polymerization by feeding the monomers used to form the latex binder to a reactor in the presence of at least one initiator and the at least one reactive polymerizablealkoxylated monomer of formula IIA, IIB, IIC or IIC-1 and polymerizing the monomers to produce the latex binder. The monomers fed to a reactor to prepare the polymer latex binder typically include at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters. In addition, the monomers can include styrene, vinyl acetate, or ethylene. The monomers can also include one or more monomers selected from the group consisting of styrene, [alpha]-methyl styrene, vinyl chloride, acrylonitrile, methacrylonitrile, ureido methacrylate, vinyl acetate, vinyl esters of branched tertiary monocarboxylic acids, itaconic acid, crotonic acid, maleic acid, fumaric acid, and ethylene. It is also possible to include C₄-C₈ conjugated dienes such as 1, 3-butadiene, isoprene or chloroprene. Typically, the monomers include one or more monomers selected from the group consisting of n-butyl acrylate, methyl methacrylate, styrene and 2-ethylhexyl acrylate. The initiator can be any initiator known in the art for use in emulsion polymerization such as ammonium or potassium persulfate, or a redox system that typically includes an oxidant and a reducing agent. Commonly used redox initiation systems are described e.g., by A. S. Sarac in Progress in Polymer Science 24 (1999) , 1149-1204. The polymer latex binder can be produced by first preparing an initiator solution comprising the initiator and water. A monomer pre-emulsion is also prepared comprising at least a portion of the monomers to be used to form the latex polymer, one or more surfactants (emulsifiers) , water, and additional additives such as NaOH. The one or more surfactants in the monomer pre-emulsion include any of the reactive polymerizablealkoxylated monomers of the present invention. The initiator solution and monomer pre-emulsion are then continuously added to the reactor over a predetermined period of time (e.g. 1.5-5 hours) to cause polymerization of the monomers and to thereby produce the latex polymer. Typically, at least a portion of the initiator solution is added to the reactor prior to adding the monomer pre-emulsion. Prior to the addition of the initiator solution and the monomer pre-emulsion, a seed latex such as a polystyrene seed latex can be added to the reactor. In addition, water, one or more surfactants, and any monomers not provided in the monomer pre-emulsion can be added to the reactor prior to adding the initiator and adding the monomer pre-emulsion. The reactor is operated at an elevated temperature at least until all the monomers are fed to produce the polymer latex binder. Once the polymer latex binder is prepared, it is typically chemically stripped thereby decreasing its residual monomer content. Typically, it is chemically stripped by continuously adding an oxidant such as a peroxide (e.g. t-butylhydroperoxide) and a reducing agent (e.g. sodium acetone bisulfite) , or another redox pair such as those described by A. S. Sarac in Progress in Polymer Science 24 (1999) , 1149-1204, to the latex binder at an elevated temperature and for a predetermined period of time (e.g. 0.5 hours) . The pH of the latex binder can then be adjusted and a biocide or other additives added after the chemical stripping step.

The coating composition according to the present invention is a stable fluid that can be applied to a wide variety of materials such as, for example, paper, wood, concrete, metal, glass, ceramics, plastics, plaster, and roofing substrates such as asphaltic coatings, roofing felts, foamed polyurethane insulation； or to previously painted, primed, undercoated, worn, or weathered substrates. The coating composition of the invention can be applied to the materials by a variety of techniques well known in the art such as, for example, brush, rollers, mops, air-assisted or airless spray, electrostatic spray, and the like.

Latex polymer compositions comprising surface active (emulsifier) alkoxylated compound

The present invention also provides the use of a surface active alkoxylated compound in a coating composition for reducing combining of coating particles on a substrate wherein the surface active alkoxylated compound can be used as an emulsifier during the emulsion polymerization reaction used to make a latex polymer.

In one aspect, the surface active alkoxylated compound of the present invention has the general formula of IIIA :

R₁, R₂ and R₃ are independently selected from:

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

n is 1-100, for example, 3 to 80, 4 to 60, 4 to 60 or 8 to 50；

wherein R is -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H_11, -OC₆H_13, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation including but not limited to H⁺, Na⁺, NH₄ ⁺, K⁺, Li⁺ or –N (R₁₁) ₄ ⁺wherein R₁₁ is a –H or a C₁-C₆ alkyl group and at least one R₁₁ is a C₁-C₆ alkyl group.

In one embodiment, n is an integer of from 4 to 80. In another embodiment, n is an integer of from 4 to 60. In still another embodiment n is an integer of from 4 to 50. In still another embodiment, n is an integer of from 8 to 50.

Typically the surface active alkoxylated compound has the formula IIIB:

wherein, R, R₁, R₂, R₃, X and n are as defined for the structure of formula IIIA. If desired, the aromatic ring shown in structural formula IIIB may be saturated.

More typically a surface active alkoxylatedtristyrylphenol, e.g., ethoxylatedtristyrylphenol, or a surface active alkoxylatedtributylphenol, e.g., ethoxylatedtributylphenol, can be used as an emulsifier during the emulsion polymerization reaction used to make latex polymer for reducing the combining of the coating particles on a substrate. The surface active ethoxylatedtristyrylphenols have the structural formula IIIC and the surface active ethoxylatedtributylphenols have the structural formula IIIC-1, respectively, as follows:

wherein, n is an integer of from 1 to 100 for example, 4 to 60 or 8 to 25；

wherein R₅ is -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H_11, -OC₆H_13, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation including but not limited to H⁺, Na⁺, NH₄ ⁺, K⁺, Li⁺ or–N (R₁₁) ₄ ⁺wherein R₁₁ is a –H or a C₁-C₆ alkyl group and at least one R₁₁ is a C₁-C₆ alkyl group.

In one embodiment, n is an integer of from 4 to 80. In another embodiment, n is an integer of from 4 to 60. In still another embodiment, n is an integer of from 10 to 50. In still another embodiment, n is an integer of from 10 to 25.

When the surface active alkoxylatedalkyldistyrylphenol, ethoxylatedtristyrylphenol or ethoxylatedtributylphenol is employed as an emulsifier in emulsion polymerization to form the latex polymer, the latex polymer is made from a mixture wherein the surface active emulsifier is utilized. In one embodiment, the emulsifier is added in an amount greater than 1.3％by weight of the polymer or monomers used to form the latex polymer, in an amount greater than 1.6％by weight of the polymer or monomers used to form the latex polymer, typically in an amount greater than about 2％by weight of the polymer or monomers used to form the latex polymer, more typically in an amount greater than about 4％by weight of the polymer or monomers used to form the latex polymer, and most typically in an amount greater than about 7.5％by weight of the polymer or monomers used to form the latex polymer. In another embodiment, the latex coating composition contains an emulsifier in an amount greater than about 8％by weight of the polymer or monomers used to form the latex polymer, or greater than about 10％by weight of the polymer or monomers. In another embodiment, the emulsifier is added is between about 1.6％and 7.5％by weight of the polymer or monomers used to form the latex polymer. In another embodiment, emulsifier added is between about 1.6％and 45％by weight of the polymer or monomers used to form the latex polymer, typically between about 1.6％and 35％by weight of the polymer or monomers used to form the latex polymer.

If desired the ethylene oxide repeating units of the ethylene oxide chain of formula IIIC or IIIC-1 may be replace by the above described - (OX) - group to form alkoxylatedtristyrylphenol or alkoxylatedtributylphenol.

The typical monomers from which the at least one latex polymer (sometimes referred to herein as first monomer) is formed are described above in the section entitled “Other Monomers” .

As described above, the polymer latex binder can be produced by first preparing an initiator solution comprising the initiator and water. A monomer pre-emulsion is also prepared comprising at least a portion of the monomers to be used to form the latex polymer, one or more surfactants (emulsifiers) , water, and additional additives such as NaOH. The one or more surfactants in the monomer pre-emulsion include the surface active alkoxylated compound of the invention. Thus, the surface active alkoxylated compound is employed as an emulsifier to form a blend rather than as a reactant which copolymerizes with the other monomers which form the polymer latex binder. The initiator solution and monomer pre-emulsion are then continuously added to the reactor over a predetermined period of time (e.g. 1.5-5 hours) to cause polymerization of the monomers and to thereby produce the latex polymer. Typically, at least a portion of the initiator solution is added to the reactor prior to adding the monomer pre-emulsion. Prior to the addition of the initiator solution and the monomer pre-emulsion, a seed latex such as a polystyrene seed latex can be added to the reactor. In addition, water, one or more surfactants, and any monomers not provided in the monomer pre-emulsion can be added to the reactor prior to adding the initiator and adding the monomer pre-emulsion. The reactor is operated at an elevated temperature at least until all the monomers are fed to produce the polymer latex binder. Once the polymer latex binder is prepared, it is typically chemically stripped thereby decreasing its residual monomer content. Typically, it is chemically stripped by continuously adding an oxidant such as a peroxide (e.g. t-butylhydroperoxide) and a reducing agent (e.g. sodium acetone bisulfite) , or another redox pair such as those described by A. S. Sarac in Progress in Polymer Science 24 (1999) , 1149-1204, to the latex binder at an elevated temperature and for a predetermined period of time (e.g. 0.5 hours) . The pH of the latex binder can then be adjusted and a biocide or other additives added after the chemical stripping step.

The incorporation of the surface active alkoxylated compound (emulsifier) in the emulsion polymerization reaction mixture enables the coating composition to have reduced combining of the coating particles on the substrate.

Additive

In another aspect, the above described surface active alkoxylated compound of structural formula IIIA, IIIB, IIIC or IIIC-1 can be used as a coagulation reducing additive to the coating composition for reducing combining of the coating particles on the substrate. In one particular embodiment, the above described surface active alkoxylated compound of structural formula IIIA, IIIB, IIIC or IIIC-1 can be used as a coagulation reducing additive to an already formed aqueous dispersion of at least one latex polymer. It is understood, that the coagulation reducing additive can be added any point in the production of the coating composition, including but not limited to during the emulsification step, during formulation, etc. It is also understood that the coagulation reducing additive can be post-added to the coating composition.

In one embodiment, this results in a coating composition, in particular an aqueous coating composition, comprising the surface active alkoxylated compound of the present invention. When the surface active alkoxylated compound is employed as an additive to an already formed aqueous latex dispersion, the resulting composition has the surface active alkoxylated compound additive in an amount of about 1 to 10, Typically 2 to 8 or 2 to 6, parts per 100 parts by weight of monomers used to form the latex polymer.

The typical monomers from which the latex polymer is formed are described above in the section entitled “Other Monomers” and can be copolymerized with the reactive polymerizablealkoxylated monomers of the present invention as described above.

In one embodiment, the coagulation reducing additive comprises a blend of two or more surface active alkoxylated compounds each of formula IIIA, IIB, IIIC or IIIC-1. In another embodiment, the coagulation reducing additive comprises a blend of:

(i) at least one non-ionic surfactant having formula:

wherein, n is an integer of from 1 to 100；

wherein R₅ is selected from the group consisting of a C₁-C₁₂ alkyl group, a C₁-C₁₂hydroxyalkyl group, a C₁-C₁₂cycloalkyl group, a C₁-C₁₂ aryl group, -Cl, -Br, -CN, -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H_9, -OC₅H_11, and-OC₆H₁₃；

and

(ii) at least one anionic surfactant having formula:

wherein, n is an integer of from 1 to 100；

wherein R₅ is selected from the group consisting of alkylphosphonate, alkylphosphate, alkylsulfate, alkylsulfonate, phosphonate, phosphate, sulfate, sulfonate, carboxylate and any salt thereof.

The present invention further includes a method for reducing combining of coating particles on a substrate, comprising adding one or a blend of surface active alkoxylated compound surfactant (s) (emulsifier (s)) of structural formula IIIA, IIIB, IIIC and/or IIIC-1 as described above to an aqueous dispersion of a latex polymer to produce the latex binder. The at least one pigment and other additives can then be mixed with the resulting latex binder to produce the aqueous coating composition in any appropriate order. The addition of the surface active alkoxylated compound of formula IIIA, IIIB, IIIC or IIIC-1 to the latex polymer forms a mixture having a lower VOC content.

In another embodiment, the present invention is a method for reducing combining of coating particles on a substrate comprising adding to a coating composition an effective amount of a surface active alkoxylated compound additive of formula IIIA, IIIB, IIIC or IIIC-1. In a preferred embodiment, the surface active alkoxylated compound additive is a blend of:

(i) at least one non-ionic surfactant having formula:

wherein, n is an integer of from 1 to 100, wherein R5 is selected from the group consisting of a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -Cl, -Br, -CN, -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H_9, -OC₅H_11, and-OC₆H₁₃；

and

(ii) at least one anionic surfactant having formula:

wherein n is an integer of from 1 to 100；

When the surface active alkoxylated compound is employed as an additive to an already formed paint or an already formed coating composition, e.g., an aqueous latex coating dispersion, the resulting composition has the surface active alkoxylated compound additive typically in an amount greater than about 1.3％by weight of the polymer or monomers used to form the latex polymer, more typically in an amount greater than about 1.6％by weight of the polymer or monomers used to form the latex polymer, yet more typically in an amount greater than about 2％by weight of the polymer or monomers used to form the latex polymer, even more typically in an amount greater than about 4％by weight of the polymer or monomers used to form the latex polymer, and most typically in an amount greater than about 7.5％by weight of the polymer or monomers used to form the latex polymer. In another embodiment, the latex coating composition contains surface active alkoxylated compound in an amount between about 1.6％and 7.5％by weight of the polymer or monomers used to form the latex polymer. In another embodiment, the latex coating composition contains surface active alkoxylated compound in an amount between about 1.6％and 45％by weight of the polymer or monomers used to form the latex polymer, typically between about 1.6％and 35％. Pigment is a typical additive, for example, added during formulation of paint from raw aqueous latex polymer dispersion.

Other Additives

The aqueous coating composition of the present invention includes at least one latex polymer derived from at least one monomer, for example an acrylic monomer and/or any of the other above described latex monomers. The aqueous coating composition of the invention includes less than 2％by weight and typically less than 1.0％by weight of anti-freeze agents based on the total weight of the aqueous coating composition. More typically, the aqueous coating composition is substantially free of anti-freeze agents.

The aqueous coating composition typically includes at least one pigment. The term "pigment" as used herein includes non-film-forming solids such as pigments, extenders, and fillers. The at least one pigment is typically selected from the group consisting of TiO₂ (in both anastase and rutile forms) , clay (aluminum silicate) , CaCO₃ (in both ground and precipitated forms) , aluminum oxide, silicon dioxide, magnesium oxide, talc (magnesium silicate) , barytes (barium sulfate) , zinc oxide, zinc sulfite, sodium oxide, potassium oxide and mixtures thereof. Suitable mixtures include blends of metal oxides such as those sold under the marks MINEX (oxides of silicon, aluminum, sodium and potassium commercially available from Unimin Specialty Minerals) , CELITES (aluminum oxide and silicon dioxide commercially available from Celite Company) , ATOMITES (commercially available from English China Clay International) , and ATTAGELS (commercially available from Engelhard) . More typically, the at least one pigment includes TiO₂, CaCO₃ or clay. Generally, the mean particle sizes of the pigments range from about 0.01 to about 50 microns. For example, the TiO₂ particles used in the aqueous coating composition typically have a mean particle size of from about 0.15 to about 0.40 microns. The pigment can be added to the aqueous coating composition as a powder or in slurry form. The pigment is typically present in the aqueous coating composition in an amount from about 5 to about 50 percent by weight, more typically from about 10 to about 40 percent by weight.

The aqueous coating composition can optionally contain additives such as one or more film-forming aids or coalescing agents. Suitable firm-forming aids or coalescing agents include plasticizers and drying retarders such as high boiling point polar solvents. Other conventional coating additives such as, for example, dispersants, additional surfactants (i.e. wetting agents) , rheology modifiers, defoamers, thickeners, biocides, mildewcides, colorants such as colored pigments and dyes, waxes, perfumes, co-solvents, and the like, can also be used in accordance with the invention. For example, non-ionic and/or ionic (e.g. anionic or cationic) surfactants can be used to produce the polymer latex. These additives are typically present in the aqueous coating composition in an amount from 0 to about 15％by weight, more typically from about 1 to about 10％by weight based on the total weight of the coating composition.

As mentioned above, the aqueous coating composition in some embodiments can include less than 2.0％of VOC agents based on the total weight of the aqueous coating composition. Exemplary agents include ethylene glycol, diethylene glycol, propylene glycol, glycerol (1, 2, 3-trihydroxypropane) , ethanol, methanol, 1-methoxy-2-propanol, 2-amino-2-methyl-1-propanol, and FTS-365 (a freeze-thaw stabilizer from Inovachem Specialty Chemicals) . More typically, the aqueous coating composition includes less than 1.0％or is substantially free (e.g. includes less than 0.1％) of anti-freeze agents. Accordingly, the aqueous coating composition of the invention typically has a VOC level of less than about 100 g/L and more typically less than or equal to about 50 g/L.

The aqueous coating composition of the invention can be subjected to freeze-thaw cycles using ASTM method D2243-82 or ASTM D2243-95 without coagulation.

The balance of the aqueous coating composition of the invention is water. Although much of the water is present in the polymer latex dispersion and in other components of the aqueous coating composition, water is generally also added separately to the aqueous coating composition. Typically, the aqueous coating composition includes from about 10％to about 85％by weight and more typically from about 35％to about 80％by weight water. Stated differently, the total solids content of the aqueous coating composition is typically from about 15％to about 90％, more typically, from about 20％to about 65％.

The coating composition is typically formulated such that the dried coatings comprise at least 10％by volume of dry polymer solids, and additionally 5 to 90％by volume of non-polymeric solids in the form of pigments. The dried coatings can also include additives such as plasticizers, dispersants, surfactants, rheology modifiers, defoamers, thickeners, biocides, mildewcides, colorants, waxes, and the like, that do not evaporate upon drying of the coating composition.

In one preferred embodiment of the invention, the aqueous coating composition is a latex paint composition comprising at least one latex polymer derived from at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters and at least one polymerizablealkoxylatedsurfactant； at least one pigment and water. As mentioned above, the at least one latex polymer can be a pure acrylic, a styrene acrylic, a vinyl acrylic or an acrylated ethylene vinyl acetate copolymer.

According to the present invention, the alkoxylated compounds can be used for reducing combining of coating particles on a substrate. In one embodiment, the substrate is a coating applying apparatus, such as a brush, a roller, and a mop. In one embodiment, the coating applying apparatus is subject to acidic treatment prior to coming into contact with the coating composition. In another embodiment, the substrate is an article or a material which is subject to coatings or paints, such as paper, wood, concrete, metal, glass, ceramics, plastics, plaster, an asphaltic coating, a roofing felt, foamed polyurethane insulation, or a previously painted, primed, undercoated, worn, or weathered article.

The following examples are included to illustrate embodiments of the invention. Needless to say, the invention is not limited to the described examples.

Examples

The following examples illustrate the coagulation reducing effects of the alkoxylated compounds of the present invention. In the examples, In the examples, a blend of an anionic TSP ethoxylate surfactant (33 wt％) and a non-ionic TSP ethoxylate surfactant (66 wt％) was used.

Example 1

Paint composition samples were prepared according to the formulations shown in Table 1. The above mentioned blend was post added to the paint compositions in comparison to a normal wetting agent (Triton X405) and water.

Table 1

The paint compositions were diluted in water and maintained overnight. Then, a brush was immersed in the paint composition samples respectively and kept at 25 ℃ for 24 hours. Subsequently, the brush was drawn out and the softness of the brush hair was evaluated immediately. The results are shown in Table 2 below.

As shown in Table 2, compared to the brush immersed in the paint composition sample without the blend according to the present invention (Comparative Samples 1 and 2) , the brush immersed in the paint composition sample containing the blend (Sample 1) showed higher softness, indicating that less coagulation of coating particles were formed on such brush.

Table 2

	Softness
	Softness	Sample 1	+++
Comparative Sample 1	++	Sample 1	+++
Comparative Sample 1	++	Comparative Sample 2	+

( “+++” represents the highest softness and "+" represents the lowest softness. The softness was scored by a panel in a double blinded manner) .

Example 2

In this experiment, latex composition samples were prepared according to the formulations shown in Table 3.

Table 3

The latex compositions were diluted in water and maintained overnight. Then, a brush was immersed in the latex composition samples respectively and kept for 24 hours. Subsequently, the brush was drawn out and the softness of the brush hair was observed by eyes and evaluated.The results are shown in Table 4 below.

Table 4

As shown in Table 4, compared to the brush immersed in the latex composition samples without the blend according to the present invention (Comparative Samples 3 and 4) , the brush immersed in the latex composition sample containing the blend (Sample 2) showed higher softness, indicating that less coagulation of coating particles were formed on such brush.

Claims

Use of a compound having the general formula of IA for reducing combining of coating particles on a substrate :

wherein B is a 5 or 6 membered cycloalkyl ring or a single ring aromatic

hydrocarbon having a 6 membered ring；

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is C₂H₄, C₃H₆, or C₄H_8, or X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is an integer of from 1 to 100；

wherein R is selected from an ethylenically unsaturated group, -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H₁₁, -OC₆H₁₃, -Cl, -Br, -CN, Phosphonate (-PO_3-M⁺) , Phosphate (PO_4-M⁺) , Sulfate (SO_4-M⁺) , Sulfonate (SO_3-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+is a cation.
The use according to claim 1, wherein the compound has the general formula of IB :

wherein R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is C₂H₄, C₃H₆, or C₄H_8, or X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is an integer of from 1 to 100；

wherein R is selected from an ethylenically unsaturated group, -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H₁₁, -OC₆H₁₃, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+is a cation.
Use of a monomer (second monomer) having the general formula of IIA for reducing combining of coating particles on a substrate wherein the second monomer is copolymerized with at least one first monomer into the backbone of a latex polymer used for forming a coating composition:

wherein B is a 5 or 6 membered cycloalkyl ring or a single ring aromatic hydrocarbon having a 6 membered ring；

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is C₂H₄, C₃H₆, or C₄H_8, or X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is an integer of from 1 to 100；

wherein R is an ethylenically unsaturated group.
The use according to claim 3, wherein the second monomer has the general formula of IIB :

wherein R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is C₂H₄, C₃H₆, or C₄H_8, or X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is an integer of from 1 to 100；

R is an ethylenically unsaturated group.
The use according to claim 4, wherein the second monomer has the general formula of IIC or IIC-1:

wherein n is an integer of from 1-100；

R₄ is a member of the group consisting of H, C₁-C₈hydroxy alkyl, C₁-C₆ alkyl.
Use of an additive in a coating composition for reducing combining of coating particles on a substrate wherein the additive comprises at least one compound having the general formula of IIIA :

wherein B is a 5 or 6 membered cycloalkyl ring；

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is at least one member of the group consisting of C₂H₄, C₃H₆, and C₄H₈, or wherein X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms； n is 1-100；

wherein R is -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H₁₁, -OC₆H₁₃, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation.
The use according to claim 6, wherein the compound has the general formula of IIIB :

wherein R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is at least one member of the group consisting of C₂H₄, C₃H₆, and C₄H₈, or wherein X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is 1-100；

wherein R is -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H₁₁, -OC₆H₁₃, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation.
The use according to claim 6, wherein the compound has the general formula of IIIC or IIIC1:

wherein n is an integer of from 1 to 100；

R₅ is -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H₁₁, -OC₆H₁₃, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation.
The use according to any one of claims 6 to 8, wherein the cation is H⁺, Na⁺, NH₄ ⁺, K⁺, Li⁺ or–N (R₁₁) ₄ ⁺wherein R₁₁ is a –H or a C₁-C₆ alkyl group and at least one R₁₁ is a C₁-C₆ alkyl group.
The use according to claim 6, wherein the additive is a blend of (i) at least one non-ionic surfactant having formula:

wherein, n is an integer of from 1 to 100；

R₅ is selected from the group consisting of a C₁-C₁₂ alkyl, hydroxyalkyl,

cycloalkyl, aryl or aralkyl, -Cl, -Br, -CN, -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H_9, -OC₅H_11, and-OC₆H₁₃； and

(ii) at least one anionic surfactant having formula:

wherein, n is an integer of from 1 to 100；

R₅ is selected from the group consisting of alkylphosphonate, alkylphosphate, alkylsulfate, alkylsulfonate, phosphonate, phosphate, sulfate, sulfonate, carboxylate and any salt thereof.
A method for reducing combining of coating particles on a substrate by including in a coating composition a compound having the general formula of IA :

wherein B is a 5 or 6 membered cycloalkyl ring or a single ring aromatic hydrocarbon having a 6 membered ring；

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is C₂H₄, C₃H₆, or C₄H_8, or X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is an integer of from 1 to 100；

wherein R is selected from an ethylenically unsaturated group, -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H₁₁, -OC₆H₁₃, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+is a cation.
A method for reducing combining of coating particles on a substrate comprising the step of copolymerizing a monomer (second monomer) having the general formula of IIA with at least one first monomer into the backbone of a latex polymer used for forming a coating composition:

wherein B is a 5 or 6 membered cycloalkyl ring or a single ring aromatic hydrocarbon having a 6 membered ring；

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is C₂H₄, C₃H₆, or C₄H_8, or X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is an integer of from 1 to 100；

wherein R is an ethylenically unsaturated group.
A method for reducing combining of coating particles on a substrate comprising the step of adding in a coating composition an additive comprising at least one compound having the general formula of IIIA :

wherein B is a 5 or 6 membered cycloalkyl ring；

R₁, R₂ and R₃ are independently selected from:

a C₁-C₁₈ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, -H,

with the proviso that at least one of R₁, R₂ and R₃ is not –H；

wherein, X is at least one member of the group consisting of C₂H₄, C₃H₆, and C₄H₈, or wherein X is a divalent hydrocarbon radical selected from linear or branched alkylene radicals having from 2 to 8 carbon atoms；

n is 1-100；

wherein R is -OH, -OCH₃, -OC₂H₅, -OC₃H₇, -OC₄H₉, -OC₅H₁₁, -OC₆H₁₃, -Cl, -Br, -CN, Phosphonate (-PO₃ ^-M⁺) , Phosphate (PO₄ ^-M⁺) , Sulfate (SO₄ ^-M⁺) , Sulfonate (SO₃ ^-M⁺) , carboxylate (COO^-M⁺) , a C₁-C₁₂ alkyl, hydroxyalkyl, cycloalkyl, aryl or aralkyl, wherein M+ is a cation.
The use according to any one of claims 1 to 10 or the method according to any one of claims 11 to 13, wherein the substrate is a coating applying apparatus.
The use according to any one of claims 1 to 10 or the method according to any one of claims 11 to 13, wherein the substrate is a coating applying apparatus which is subject to acidic treatment prior to coming into contact with the coating composition.