ES2358677T3 - WATERPROOF DISPERSION OF POLI (ACETAL-POLYETHER) AND ITS USE IN PROTECTIVE COATINGS. - Google Patents

Abstract

An aqueous polymer dispersion comprising: a) hydrophobic modified poly (acetal- or ketal-polyether) (b) water, and c) a viscosity reducing agent chosen from the group consisting of i ) an ethoxylated alcohol having a C9-12 hydrocarbon residue component, ii) an ethoxylated acetylene diol, iii) a phosphate ester iv) a combination of ethoxylated alcohol and anionic dialkyl sulphosuccinate, and v) a combination of ethoxylated alcohol and an anionic phosphate ester.

Description

This application claims the benefit of the Provisional Application of the United States with Serial No. 60 / 634,500, filed on December 9, 2004 and of the Provisional Application of the United States with Serial No. 60 / 636,268 filed on December 15, 2004.

FIELD OF THE INVENTION

This invention relates to an aqueous dispersion of an associative thickener and at least one surfactant. More particularly, the present invention relates to an aqueous dispersion of an associative thickener based on poly (acetal- or ketal-polyether) (PAPE) and at least one surfactant chosen from alcohol ethoxylate, ethoxylated acetylenic diols, phosphate esters and dialkyl sulfosuccinates. This invention further relates to the use of these aqueous dispersions in aqueous coating compositions.

BACKGROUND OF THE INVENTION

In general, the associative thickeners are water soluble or water dispersible polymers having a small amount of hydrophobic groups. They are widely used to control the rheology and application properties of a wide variety of aqueous systems. One of the main areas of application of associative thickeners is in aqueous coatings. It is well known that associative thickeners that are used as rheology modifying agents in aqueous coatings are difficult to prepare in the form of highly concentrated aqueous solutions, with low viscosity such as to allow creep, pumping and dosing in aqueous systems such as coatings. aqueous protectors. The mechanism through which associative thickeners induce thickening of the aqueous phase may include hydrophobic associations between hydrophobic groups of thickener molecules and / or interaction of associative thickeners with hydrophobic components present in aqueous coating compositions. The different types of associative thickeners are based on modified natural polymers, such as cellulose ethers that have been hydrophobically modified, synthetic polymers, such as hydrophobic modified ethoxylated polyurethanes (HEUR), hydrophobicly modified alkali soluble emulsions ( HASE) and hydrophobic modified poly (acetal- or ketal-polyethers) (HM-PAPE). The paint performance properties of aqueous coatings formulated with associative thickeners vary based on their most fundamental properties such as thickening efficiency, bleed, color equalization and film formation (ICI viscosity).

In recent years, associative thickeners have gained importance, particularly for the control of the rheology of aqueous coatings and latex paints. Because synthetic associative thickeners are prepared from basic chemicals, they can be prepared with certain properties provided in advance. In other words, from the first layer they can exhibit the desired properties. Synthetic associative thickeners perform various functions in aqueous systems. For example, in latex paints and aqueous coatings, the thickener provides better pigment stability and suspension, as well as better rheology and application properties. In personal hygiene products, the thickener provides a better sensation to the touch, softness and richness of the product, giving it an aesthetically more pleasant sensation. In other industries, associative thickeners are used to improve other desired properties.

The control of the viscosity of the polymer solution and the possibility of incorporating polymers in the solution with a high percentage of solids content with relatively low viscosity are important requirements from the point of view of manufacture and application. These requirements allow to balance the total cost of use of the product and achieve appropriate procedures for the incorporation of the product in the application formulation. Examples of these synthetic associative thickeners that are employed as rheology modifying agents in aqueous coatings include hydrophobic modified ethoxylated urethane (HEUR), hydrophobic modified alkali soluble emulsion (HASE), hydrophobic modified polyethylene glycol (HM) -PEG) and hydrophobic modified poly (acetal- or ketalpolyether) (HM-PAPE).

Due to the intermolecular association through hydrophobic groups, aqueous solutions of associative thickeners exhibit high viscosities even at low concentrations. To avoid the viscosity of the solution of the different types of associative thickeners, viscosity suppression aids such as propylene glycol, butylcarbitol, cyclodextrins and surfactants are used (see US 6,063,857; US 5,137,571; US 5,425. 806; US 6,150,445; US 5,378,756; US 5,959,013; US 5574127; US 6162877). Typical and useful viscosity ranges for these aqueous combinations of thickener and additives are approximately 1000 cps to 5000 cps. Typical polymer concentrations desired are within the range of about 15 to 30% by weight.

The HM-PAPE product, manufactured and marketed by Hercules Incorporated under the trade name of Aquaflow®, is supplied to customers in liquid form. Currently, some of these products are marketed as solutions with 25% active polymer in a mixture of water and butylcarbitol.

Existing Aquaflow products are moderated in order to avoid incorporation into a high-gloss paint mixture that contains a styrene-acrylic binder. This problem also applies to aqueous coatings that do not contain solvents, that have a 70% volume pigment (PVC) concentration and that contain a vinyl acetate / ethylene latex (VAc / E).

Taking into account the experience of the clients themselves, it has been proven that most of the manufacturers of latex paints found difficulties in incorporating synthetic associative thickeners in the paint formula. Ideally, once the thickener has been added to the base paint, the resulting mixture should be easy to stir and the thickener should manifest its thickening ability very quickly, preferably over several minutes. In this way, the complete viscosity of the paint is achieved relatively quickly and no increase in viscosity occurs during storage.

The ease of incorporation of the thickener in latex paints is measured by recording the time it takes to produce the thickening effect of the paint formulation and by the time in which no change in viscosity is observed. After incorporating the thickener into the base paint, its appearance should be smooth, which means that lumps should not be appreciated in any way. Subsequently, the viscosity of the resulting paint is measured. In the paint industry, viscosity refers to the Stomer viscosity and is measured in units of Krebs (KU).

Since associative thickeners contain hydrophobic groups, they have the ability to form intermolecular associations through their hydrophobic groups. They can also be adsorbed on hydrophobic surfaces of dispersed particles, such as latexes and pigments. As a result, associative thickeners have a thickening effect much greater than the corresponding polymer having the same molecular weight and containing no hydrophobic groups. A method for solving the problem of high viscosity is known in the art. It involves dissolving the association thickener in water and then adding the solution to the aqueous formulation. However, the approach restricts the amount of polymer that can be dissolved in a given amount of water without producing a very high viscosity. Another approach to avoid the formation of a high viscosity is to prepare an associative thickener dispersion normally with an organic solvent. However, this approach should be avoided as organic solvents are volatile and many of them can cause damage to the environment. Another approach to reduce the viscosity of aqueous solutions of associative thickeners is to add nonionic surfactants to aqueous solutions of associative thickeners.

Several patents are known that disclose the preparation of aqueous solutions with creep capacity or dispersions of associative thickeners that employ surfactants. US Patent No. 5,425,806 discloses an aqueous dispersion of an associative thickener with a reduced volatile organic compound (VOC) content that can flow at 25 ° C. The dispersion includes 15-40% by weight of an associative thickener (i.e. polyurethanes, polyesters, modified cellulosic materials, polyester urethanes, polyether alpha-olefins and polyether polyols), 3085% by weight of water and 1-30 % by weight of one or more anionic or non-ionic surfactants. US Patent No. 5,378,756 discloses a thickener composition of a polyurethane polymer, a non-ionic emulsifier and a compound containing an acetylenic group (a triple bond) in the medium. U.S. Patent No.

6,150,445 discloses an aqueous concentrate of 10-50% by weight of an associative thickener of polyurethane and 1-25% by weight of a non-ionic surfactant containing ethyleneoxy and propyleneoxy groups. U.S. Patent No.

6,083,857 discloses a water composition, at least 5% by weight of hydrolyzed and neutralized alkali soluble emulsion polymer modified and less than 0.5% by weight of a surfactant. None of these prior techniques disclose the present invention.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to an aqueous dispersion of a hydrophobic modified poly (acetal- or ketal-polyether) (HM-PAPE), and a viscosity reducing agent of at least one alcohol ethoxylated surfactant having a C9-12 alcohol component, an ethoxylated acetylene diol surfactant, phosphate ester surfactant, a combination of ethoxylated alcohol with anionic dialkyl sulphosuccinate surfactant or a combination of ethoxylated alcohol with anionic phosphate ester surfactant.

This invention also relates to a protective aqueous coating containing the aforementioned dispersion and optionally a latex.

This invention also relates to an improved method for incorporating an HM-PAPE thickener into a protective coating formulation, in which the dissolution time of HM-PAPE is considerably reduced compared to the dissolution time of HM -PAPE relative to high solids solutions prepared using water only or together with an organic solvent, such as butyl alcohol.

DETAILED DESCRIPTION OF THE INVENTION

It has just been discovered that poly (acetal- or ketal-polyethers) (HM-PAPE) can be effectively dispersed in water with a solids concentration of 40% by weight, preferably 30% by weight, and still have a viscosity low acceptable with the addition of only 0.5-3.0% by weight of non-ionic and / or anionic viscosity reducing agent.

ASSOCIATIVE THICKENERS

The types of associative thickeners that are within the scope of the present invention are based on a poly (acetal- or ketal-polyether) (PAPE) main chain. Types of thickeners include poly (acetalcetal-polyether) with hydrophobic termination and hydrophobicly modified comb polymers described in US Patents 5,574,127 and 6,162,877, respectively. Another class of associative thickeners based on PAPE that are within the scope of the present invention includes modified PAPE of alkaryl glycidol ether (disclosed in the non-provisional application with serial number 11/031, 187, entitled "Colorant Compatible Syntehtic Thickener For Saint ”, Issued on January 7, 2005, for PAPE in the form of a hydrophobic comb (or blocks) modified (X-33487-45; X-33445-70). In addition, the dispersion may also include a mixture of the above PAPE based on polymers and other commercially available associative thickeners, such as HEUR, HASE, HM-PEG and hydrophobically modified cellulosic ethers.

The composition of the present invention has a poly (acetalcetal-polyether) (PAPE) main chain that is linear or branched, which is linear. Polyethers (as precursors of the final polymer) that can be used in the present invention include any water soluble poly (alkylene oxide) or copolymers of poly (alkylene oxide); The preferred polyether main chain is a poly (alkylene oxide) or water soluble copolymers of ethylene oxide with another co-monomer such as propylene oxide and butylene oxide.

In accordance with the present invention, the aqueous dispersion of HM-PAPE is a hydrophobically modified poly (acetalcetal polyether) in the terminal position. The HM-PAPE has terminal hydrophobic groups and can also have hanging hydrophobic groups in that area. The hydrophobic groups may be an alkyl moiety having 3 to 30 carbon atoms or an alkylaryl moiety such as a methylphenyl group. The hydrophobic group can be linear or branched. Hanging hydrophobic groups can hang from the main chain following a uniform pattern, a random pattern or in the form of clusters.

The weight average molecular weight of the HM-PAPE polymer has an upper limit of 100,000, preferably 50,000 and more preferably 40,000. The lower limit of the molecular weight of the polymer is 3,000, preferably 4,000, and more preferably 8,000.

For a more detailed description of these associative polymers and processes for preparing them, for HMPAPE, see United States Patent No. 5,574,127 and United States Patent 6,162,877, and the non-provisional patent application with serial number 11 / 031, 187, entitled "Colorant Compatible Synthetic Thickener For Saint", issued on January 7, 2005, for PAPE in the form of a comb (or block) hydrophobically modified. The subject matter of these patents and patent application will be referred to herein as "HM-PAPE".

VISCOSITY REDUCING AGENT

In accordance with the present invention, typical viscosity reducing agents include nonionic and anionic surfactants. Nonionic surfactants include alcohol ethoxylates (C10- (EO) 6 - Iconol DA-6 (EO = ethylene oxide unit) Ethal DA-6 and Hunstman DA-6; C10- (EO) 9 - Ethal DA- 9; C9-11 (EO) 6 - Rhodasurf 91-6), 2,4,7,9 tetramethyl-5-decin-4,7-diol ethoxylated or Surfynol 465 (Air Products); C6 alkylglycoside (AG 6206, Akzo-Nobel); C8 alkylglycoside (AG 6202, Akzo-Nobel); C8-C10 alkylglycoside (AG 6210, Akzo-Nobel); ethoxylated alcohol C10 PEG (7EO), Biodac 710 (Sasol); ethoxylated C10 PET alcohol (8EO). Biodac 810.

(Sasol); Primary alcohol ethoxylate, C9-C12 PEO (6), Synperonic 91/6 (ICI); decyl glycoside, Plantacare 200 UP (Henkel).

Typical anionic surfactants include dialkyl sulphosuccinate (diamyl sulphosuccinate - Aerosol AY100; diisobutyl sulfosuccinate - Aerosol IB-45; dioctyl sulfosuccinate - Aerosol OT); dihexyl sulfosuccinate, dispil SUS IC 680, Henkel; phosphate ester - Strodex LFK-70. The less volatile solvent of interest includes Ecosoft PB or EPB product (10.5% weight of VOC), which is monobutyl ether of tetraethylene glycol, manufactured by Dow Chemical Company, other less volatile solvents include butyl triglycol (53% by weight of VOC) (DOW) The standard solvent with high VOC content used in the industry is butyl carbitol (BC) which has a 100% VOC content. The VOC content of the solvents is calculated according to the EPA-24 test.

In the present invention, the viscosity reducing agent has an upper limit of 20% by weight, preferably 10% by weight. The lower limit may be 0.5% by weight, preferably 1.0% by weight, and more preferably 3.0% by weight. It should be noted that certain solvents can also be used as viscosity reducing agents.

WATER CONTENT

In accordance with the present invention, water may be present up to an upper limit of 85% by weight, preferably 75% by weight and more preferably 65% by weight. The lower limit of the amount of water in the dispersion is 30% by weight, preferably 40% by weight and more preferably 50% by weight. It should be understood that water is in relation to the other ingredients of the dispersions and may vary somewhat depending on the other ingredients that are present.

WATERPROOF PROTECTIVE COATINGS

In accordance with the present invention, comb-shaped or HMPAPE or HM block compositions can be used in film-forming coating compositions, such as aqueous coatings (ie, lacquers, latex paints, etc.). In latex paints, the pigment, for example, can be hydrated aluminum oxide, barium sulfate, calcium silicate, clay, silica, talc, titanium dioxide or zinc oxide. The pigment is determined by the desired results and by the manufacturer. In general, the ratio of the volume of pigment to the volume of nonvolatile material present in the paint refers to the concentration of pigment in volume (PVC), which is usually expressed as a percentage. Latex paints have an upper PVC limit of 85, preferably 75 and more preferably 65. These latex paints have a lower PVC limit of 10 and preferably 20. More particularly, when the latex paint is very bright , the PVC is from about 15 to about 30; When the latex paint is semi-glossy, the PVC is about 20 to about 35; and when the latex paint is matte, the PVC is from about 40 to about 85. Similarly, for latex paints, the ICI viscosity value should be greater than about 1.0, preferably greater than 1.5 Pa · s to get a good performance.

The improved method of the present invention based on incorporating aqueous HM-PAPE dispersions into protective coating formulations is simply to add the polymer dispersion to the coating formulation under stirring. It was surprising to see that the dissolution time of the HM-PAPE polymer was considerably reduced with respect to the dissolution time of HM-PAPE in water alone, when it was supplied as an aqueous dispersion at room temperature. In addition, the use of the aqueous dispersion of the present invention makes it easier and faster to incorporate the thickener into the paint formulation. It was found that the use of the aqueous dispersion of the present invention decreased the polymer dissolution time by about 30%, and in some cases even up to about 50%, compared to the time required when an aqueous HM solution was used -PAPE to thicken the coating formulation.

In accordance with the present invention, the incorporation of HM-PAPE polymers in the paint formulations employing the dispersions of the present invention provides several advantages. 1) Reducing the active content from 25% to 17.5% of the HM-PAPE dispersions in water / BTG (BTG = butyl triglycol) / HM-PAPE of the present invention decreased the dissolution time of the thickener in the paint by 50 %, when applied on a high gloss paint formulation. When the same dispersion was applied on a matte paint formulation, the dissolution time was reduced by 30%. 2) Another improvement of further decrease in dissolution time by another 60% is obtained using a dispersion of BTG and a surfactant (for example product of Surfynol® 465) as a viscosity decrease agent. Again, in a high gloss paint formulation, the addition of Surfynol 465 surfactant to existing commercial polymers of the Aquaflow NLS series greatly improves ease of incorporation. The addition of 1% Surfynol 465 surfactant decreases the total dissolution time of Aquaflow NLS 210 polymer in the high gloss paint by 40%. Similarly, in a latex paint with a PVC value of 70, the total dissolution time of Aquaflow NLS 210 polymer is reduced by 35% after the addition of 1% Surfynol 465 surfactant by weight over the dispersion of Aquaflow NLS 210 polymer.

Other ingredients commonly found in paints are binders (for example, 100% acrylics, vinyl acrylics and styrene acrylics), dispersants (for example, polyphosphates, amino alcohols and acrylic co-polymers), defoamers (for example , of the silicone and non-silicone type), wetting agents (for example, ethylene glycol, propylene glycol and hexylene glycol), preservatives (for example, of the type that do not contain mercury), coalescing agents (for example, glycol ethers / esters and surfactants ), biocides, humectants, pH modifiers and dyes.

For a more detailed understanding of the invention, reference is made to the following examples, which are intended to illustrate the invention and not limit it in any case. All parts and percentages are expressed in weight unless otherwise specified.

EXAMPLES

STANDARD PROCEDURES

A. The following procedure was used to prepare aqueous dispersions of polymers in the carrier solvents studied. (Table 1-2 below).

one.

 Solid polymer, water and surfactant / solvent were combined in a vessel and heated to 70-75 ° C for 1-2 hours until the mixture melted.

2.

 The hot dispersion / melt was stirred for 1 min and placed on a rotating wheel at room temperature for 2-3 hours.

3.

 If the sample had not completely dissolved after 2-3 hours, the sample is mixed by hand with a spatula and then steps 1 and 2 are repeated. 2-3 drops of glacial acetic acid were added to the sample.

dispersion to approximate the pH to ~ 7.

Four.

 The rheology of the dispersed polymer was measured and described in a footnote of Table 1.

B. A second method used to prepare the samples used in Examples 23 to 27 was to grind the experimental HM-PAPE before dissolution with a Rect sieve. Equipped with a 0.5 mesh screen. The powder was screened through a screen of size number 30 and the particles of screen number size 30 that were retained were discarded. Solutions were prepared by weighing the ingredients and mixing them overnight using an anchor-shaped stirrer. In the case of using commercially available HM-PAPE (ie Aquaflow NLS 200 and Aquaflow NLS 210 products) the additives were weighed and stirring was carried out with an anchor-shaped agitator at maximum speed for 15 minutes. The samples were allowed to equilibrate in a water bath at 25 ° C after preparation.

Brookfield viscosities of the aqueous dispersions of the invention prepared according to procedure B mentioned above were measured and recorded in the following graphs or Tables.

Preparation of HM-PAPE block polymers (comb-shaped):

X33487-45 (PAPE, 8.6% glycidyl 2-methyl phenyl ether)

A mixture of polyethylene glycol (molecular weight ~ 8000) (600 g) and sodium hydroxide microgranules (12 g) was heated at 80 ° C for 1 h. Dibromomethane (8.8 g) was added and the resulting reaction mixture was stirred for 1

h. Glycidyl 2-methyl phenyl ether (87 g) was added and the reaction temperature was maintained at 120 ° C for 4 h. Once the reaction had cooled to room temperature, the product was collected. SEC analysis showed that the product is a polymer with a number average molecular weight (Mn) of 21,000. 1 H NMR analysis contributed the amount of hydrophobic groups incorporated of 8.6% by weight.

X33487-70 (PAPE, 10.8% glycidyl 2-methyl phenyl ether)

Similarly, using the X33487-45 process, sample X33445-70 was prepared with 600 g of PEG of Mn 8,000, 12 g of NaOH, 6.2 g of dibromo-methane and 107 g of glycidyl 2-methyl phenyl ether. The product had a molecular weight (Mn) of 12,600 and a hydrophobic group content of 10.8% by weight.

HM-PAPE polymers (NLS-200 and NHS-300) are commercial products marketed by Hercules Incorporated under the trade names of Aquaflow NLS-200 and Aquaflow NHS-300.

Preparation of a new molecule of n-butyl- (EO) 7,5-Me

100 grams of Carbowax 350 product (Me- (EO) 7.5) were heated with 15 grams of NaOH for 1 hour at 80 ° C. Then, 50 grams (0.36 mol) of butyl bromide was added to the mixture and kept at 80 ° C for 2 hours, then at 100 ° C for 4 hours. After cooling, the mixture was filtered twice to remove the salt. A total amount of product of 130 grams was collected, subsequently designated as X-33564-8A.

Typical surfactants employed in the Examples include alcohol ethoxylates (C10- (EO) 6-Iconol DA-6, Ethal DA-6 and Huntsman DA-6; C10- (EO) 9 - Ethal DA-9; C9-11- (EO) 6-Rhodesurf 91-6), dialkyl sulfosuccinates (diamyl sulfosuccinate - Aerosol AY-1 00; diisobutyl sulfosuccinate - Aerosol IB-45; dioctyl sulfosuccinate Aerosol OT), 2,4,7,9-tetramethyl -5-decin-4,7-ethoxylated diol or Surfynol 465, phosphate ester - Strodex LFK-70. The solvent of low VOC content of interest includes Ecosoft PB or EPB product (monobutyl ether of tetraethylene glycol), marketed by Dow Chemical Company.

EXAMPLES 1 TO 22

Conventional procedure A was used to prepare the test samples for these Examples and the results were collected in Tables 1 and 2.

In these Examples several samples were used that are part of the present invention: Esther 20% NLS200 (C16PAPE) or 20% 2: 1 weight / weight mixture based on NHS-300 (C12-PAPE) / X-33487-45 (see then).

The 20% NLS-200 active mixture in water resulted in a gel / paste formation. The use of the surfactants chosen as additives by only (5-8)% by weight allowed the viscosity of the 20% NLS-200 dispersion to be reduced to a value of 1,000-6,000 cps.

The 20% 2: 1 weight / weight mixture based on NHS-300 (C12-PAPE) / X33487-45 produced a gel / paste in water. The use of the surfactants chosen as additives by only 5-8% by weight allowed to reduce the viscosity of the mixture dispersion from 20% to a value of 2,000-4,000 cps.

The viscosity of the mixture of NLS-200 (solid PAPE-C16) in water-butyl carbitol is the control and polymer of HM-blocks-PAPE (X-33445-70) in water mixtures - Ecosoft PB, water - Ecosoft PB - Aerosol OT and water - AOT form part of this invention.

A mixture of 25% active HM-blocks-PAPE in water with 15% added AOT surfactant resulted in the formation of a gel. The mixture of 25% active HM-blocks-PAPE in water with 15% of EPB solvent added produced a high viscosity, within the range of 14,000-10,000 cps depending on the shear rate.

Unexpectedly, however, the mixture of 25% active HM-blocks-PAPE in water with 10% of EPB solvent added (low VOC content) and 5% of added AOT surfactant produced a very low viscosity of 2000 cps. The viscosity of the solution was even lower than the viscosity of a commercial NLS-200 product prepared with the addition of 15% organic solvent with high volatile content, butyl carbitol.

Thus, a synergy was observed in the decrease in the viscosity of HM-blocks-PAPE for the combination of Ecosoft PB (mono butyl ether of tetraethylene glycol) and Aerosol OT (AOT).

Table 1 shows the viscosity data for a 2: 1 mixture based on NHS-300 (PAPE-C12) / X-33487-45 (see below) with a single surfactant or mixture of surfactants as part of the present invention.

In the cases in which the three non-ionic surfactants were used as additives to decrease the viscosity of the mixture, additional benefits were observed when combining this surfactant with an AOT surfactant. The viscosity of the mixture in the surfactant / additive-AOT combination was lower than for each of the individual components, that is, AOT or the additive used alone in the same concentration as total concentration (AOT + additive).

Thus, a synergy is observed in the decrease in viscosity for the combination of ethoxylated non-ionic alcohol surfactants and Aerosol OT.

Table 2 below shows the viscosity data for 20% NLS-200 (PAPE-C16; commercial lot No. F-05178-AT 02, see below) in solvent-low EPB water mixture, in Strodex mixture LFK-70-water, in EPB-Strodex mixture LFK-70 - water, in EPB-Iconol DA-6-water mixture as well as for 10% NHS-300 in Water and in mixture of Strodex LFK-70 water.

The control sample - 20% HM-PAPE (NLS-200) did not dissolve in water and forms a paste / gel.

The addition of surfactants either alone (non-ionic alcohol ethoxylate - Iconol DA-6 or Stordex LFK-70 anionic phosphate ester) or in combination with EPB-solvent with low VOC content allowed dispersing and drastically reducing the viscosity of the final mixture resulting in the formation of a polymer concentrate with a viscosity within the range of 1,000-3,000 cps.

The additional Examples mentioned above illustrate the efficacy of the chosen surfactants and the chosen surfactant-EPB combinations to reduce the viscosity of the HMPAPE rheology modifiers.

The characteristics of the polymer are:

- NLS-200 (solid PAPE-C16; synthesis described in US 6,809,132 B2; October 26, 2004) - Mn = 18,000; Pm = 33,000; Lot No. F-04063-B; Mn = 18.7K; Pm = 33,800; Lot No. F-05178-AT 02 - both of Pm slightly smaller than the regular lot.

- NHS-300 (solid PAPE-C12; synthesis described in US 6,809,132 B2; October 26, 2004) - Mn = 15,400; Pm = 27,000 - lower Pm; Lot No. F-04061-A; and Pm = 35,000-38,000; Lot No. P-01016A 02.

-

HM-blocks-PAPE X-33487-45: Mn = 21,100; Pm = 38,000 - normal Pm; MePhGly ether - "block-shaped" hydrophobic groups: 8.2% by weight or 5.3 moles per mole of -OH;

-

HM-blocks-PAPE X-33445-70: MePhGly ether - "block-shaped" hydrophobic groups: 10.8% by weight or 4.1 moles per mole of -OH; Mn = 12,600; Pm = 18,400 - Pm lower.

The solvents and surfactants of the Examples were marketed by Dow (Ecosoft PB), Cytec Co. (Aerosol OT-75% active and Aerosol AY-100), BASF (Iconol DA-6; Plurafac B-26), Hunstman (DA- 6), Air Products (Surfynol 465), Ethox Co. (Ethal DA-9), Rhodia Co. (Rhodasurf 91-6 and Rhodasurf LA-12), Dexter Chemical Company (Strodex LFK-70; 70% active) as well as synthesized in its own way (new molecule).

TABLE 1

Surfactant-surfactant efficacy: additional examples

Main surfactant

Chemistry MM HLB CP (1%) or solubility Viscosity * of the mixture 2: 1 cps

Plurafac B-26 1) 15% as such 2) 10% + 5% AOT

C12-C15- (EO) x- (PO) y-H 1030-med 14 CP = 72-77 C> 1% at 25C 1) Visc., Not homog. 2) 5220 cps

RhodasurfLA-12 1) 15% as such 2) 10% + 5% AOT

CH3 (CH2) 10- (EO) 12CH2OH 714 14.4 CP = 90-100C 1) 12300 cps 2) 5803 cps

New molecule 1) 15% as such 2) 10% + 5% AOT

C4H9O- (EO) 7.5-CH3  418-med N / A CP - N / A 1) 7810 cps 2) 4620 cps

* Mixture 2: 1 = NHS-300: HM-b-PAPE (-45) at 25% by weight in water (60%) - Surfactant (10%) - AOT (5%); Viscosity for surfactant - surfactant additive are at 85 s-1; 7400 cps - 15% AOT control.

Where CP means cloud point.

An AR-1000 controlled effort rheometer was used in shear scanning mode with cone geometry and

plate at 25 ° C to generate viscosity profiles (Table 1-2). Viscosities are given at approximately 8-10 s-1

(Table 1-2).

TABLE 2

Efficacy of surfactant and surfactant-solvent of low VOC content: additional examples

Polymer

Surfactant / solvent Viscosity (10s-1), cps

NLS-200 20%

80% water Not soluble

NLS-200 20%

EPB 19% + water 61% 3K

The same as before

Strodex LFK-70 10% + water 70% 2.3K

The same as before

EPB 10% + Strodex LFK-70 9% + water 61% 1.6K

The same as before

EPB 10% + Iconol DA-6 9% + water 61% 1.2K

NHS-300 20%

80% water 4.6K

NHS-300 20%

Strodex LFK-70 12% + water 68% 2.3K

Note: Here the concentration of Strodex LFK-70 was expressed by product as such, ie correction w / o for 70% activity.

The dissolution rate can be controlled by means of the thickening efficiency and the time it took to reach the appropriate viscosity with a smooth paint appearance (without lumps).

Conventional procedure B was used to prepare and evaluate the test samples for Examples 23 to 27, below.

8

EXAMPLE 23

TABLE 3

Ease of incorporation of HMPAPE “NLS 200” mixtures in HG5 high gloss paints compared to commercial Aquaflow NLS 200

Thickener

Composition (% by weight) TE (% by weight) Time needed to begin dissolution (minutes) Time needed to complete the dissolution (minutes) Qualification of ease of incorporation

NLS 200 commercial

HMPAPE / water / BC (25/60/15) 0.10  5 10 Moderate

TK 36

HMPAPE / water / BTG (25/55/20) 0.12  eleven twenty Hard

TK 34

HMPAPE / water / Surf ynol 465 (19.5 / 72.2 / 8.3) 0.13  one 2 Easy

TK 52

HMPAPE / water / BTG (21/63/16) 0.12  2 10 Moderate

TK 54 Invention

HMPAPE / water / BTG (17.5 / 66.5 / 16) 0.14  2 5 Easy

TK 57 Invention

HMPAPE / water / BTG / Surfynol 465 (17.5 / 66.5 / 13.5 / 2.5) 0.10  one 2 Easy

TK 58 Invention

HMPAPE / water / BTG / Surfynol 465 (17.5 / 66.5 / 11/5) 0.10  one 2 Easy

The improvement in the ease of incorporation can be seen by means of samples TK 57 and TK 58 that show that the dispersion of the present invention provides the same thickening efficiency as that of commercial origin NLS 200, but requires less time to Dissolve in the paint mixture.

There is an active content effect of the thickener, compared to TK 52 and TK 54, it is easier to incorporate when a smaller amount of HMPAPE is used in the mixture.

But even another improvement is possible when a mixture of BTG / Surfynol 465 is used instead of BTG as the sole viscosity reducing agent, as demonstrated in Example 23; compare TK 54 with TK 57 and TK 58.

Example 24

Ease of incorporation of HMPAPE “NLS 200” blends into a high gloss HG 5 paint compared to commercial Aquaflow NLS 200

Thickener

Composition (% by weight) TE (% by weight) Time needed to begin dissolution (minutes) Time needed to complete the dissolution (minutes) Qualification of ease of incorporation

NLS 200 commercial

HMPAPE / water / BC 0.10 5 10 Moderate

(25/60/15)

TK 63 invention

HMPAPE / water / BTG / Surfynol 465 (20.2 / 60.6 / 16.2 / 3) 0.10 1.5  3.5  Easy

TK 64 invention

HMPAPE / water / BTG / Surfynol 465 (20.2 / 60.6 / 13.2 / 6) 0.10  1.5 3 Easy

TK 52

HMPAPE / water / BTG (21/63/16) 0.12  2 10 Moderate

Example 25

Ease of incorporation of HMPAPE “NLS 210” blends into a high gloss HG 5 paint compared to commercial Aquaflow NLS 210

Thickener

Composition (% by weight) TE (% by weight) Time needed to begin dissolution (minutes) Time needed to complete the dissolution (minutes) Qualification of ease of incorporation

NLS 200 commercial

HMPAPE / water / BC (25 / 56.2 / 18.8) 0.07  7 10 Moderate

TK 39

HMPAPE / water / BTG (20.7 / 62.3 / 17) 0.09  13 > 20 Hard

TK 43

HMPAPE / water / BC (25 / 56.2 / 18.8) 0.08  5 10 Moderate

TK 55

HMPAPE / water / BTG (17.5 / 66.5 / 16) 0.08  7 fifteen Moderate

TK 62 Invention

HMPAPE / water / BTG / Surfinol 465 (17.5 / 66.5 / 11/5) 0.15 one 2 Easy

TK 65 Invention

HMPAPE / water / BTG / Surfinol 465 (20.2 / 60.6 / 13.2 / 6) 0.09  3 4,5 Easy

NLS 210 (same lot as above)

0.07  8 fifteen Moderate

NLS 210 + 0.5% by weight Surfinol 465

0.07 10  18  Hard

Duplicate

NLS 210 + 0.5% by weight Surfinol 465 0.07 10  16  Hard

NLS 210 + 1% by weight of Surfinol 465

0.07  6.5 9 Moderate

NLS 210 + 2.5% by weight Surfinol 465

0.06  6.5 9 Moderate

NLS 210 + 5% by weight Surfinol 465

0.06 5 8 Moderate

The invention is also applicable to an HMPAPE having an alkyl chain longer than the HMPAPE in Aquaflow NLS 200 as shown in Example 25. Again, thickeners were subjected to evaluation in a high gloss paint, with a binder of styrene / acrylic. The ease of incorporation was greatly improved when a mixture of Surfynol 465 and BTG was used as viscosity reducing agents (compare TK 55 with TK 62).

The invention is also applicable to commercial NLS types: the addition of 1% by weight of Surfynol 465 to Aquaflow NLS 210 decreases the total dissolution time of the thickener by 40%.

Table 3

High gloss paint formulation (HG5)

Ingredient

Parts by weight

Water

 24.0

Dispex GA 40

12.0

Preventol D7

2.0

Dehydran 1293

2.0

Propylene glycol

 20.0

AMP 90

0.2

Thioxide R-HD2

207.9

15 minutes / 4000 rpm

Primal HG 74 D

561.2

Dehydran 1293

1.0

Dowanol DPnB

22.5

Propylene glycol

 10.0

H2O / polymer

 137.2

Total

 1000

RAW MATERIAL

FUNCTION CHEMICAL DESCRIPTION SUPPLIER

Dispex GA 40

Dispersant Acrylic co-polymer, ammonium salt Ciba Specialty Chemicals

Preventol D7

Preservative Formaldehyde formulation, aqueous, isothiazolinone free Bayer

Dehydran 1293

Defoaming 10% polydimethyl siloxane solution Cognis

Propylene glycol

Co-solvent  Propylene glycol ---

AMP 90

PH stabilizer / dispersant Aminopropanol  Angus Chemie

Thioxide R-HD2

Pigment Titanium dioxide Hunstman

Primal HG 74 D

Binder Modified acrylic latex (42%) Rohm and Haas

Dowanol DPnB

Coalescence Agents Dipropylene glycolbutyl ether  Dow Chemical

This invention is also applicable for matte paint formulations. This is quite unexpected since the interaction of the associative thickener in matte type paints is quite different from that corresponding in gloss type paints.

Example 26

Ease of incorporation of HMPAPE “NLS 200” blends into a 70 SF / Mowilith LDM 1871 PVC paint

Thickener

Composition (% by weight) TE (% by weight) Time needed to begin dissolution (minutes) Time needed to complete the dissolution (minutes) Qualification of ease of incorporation

NLS 200 commercial

HMPAPE / water / BC (25/60/15) 0.43  4 8 Moderate

TK 52

HMPAPE / water / BTG (21/63/16) 0.50  one 5 Easy

TK 54 Invention

HMPAPE / water / BTG (17.5 / 66.5 / 16) 0.53  one 5 Easy

TK 57 Invention

HMPAPE / water / BTG / Surfynol 465 (17.5 / 66.5 / 13.5 / 2.5) 0.38  one 3 Easy

TK 58 Invention

HMPAPE / water / BTG / Surfynol 465 (17.5 / 66.5 / 11/5) 0.37  one 3 Easy

TK 63 Invention

HMPAPE / water / BTG / Surfynol 465 (20.2 / 60.6 / 16.2 / 3) 0.40  one 5 Easy

TK 64 Invention

HMPAPE / water / BTG / Surfynol 465 (20.2 / 60.6 / 13.2 / 6) 0.39  one 3 Easy

Example 27

Ease of incorporation of HMPAPE “NLS 210” mixtures in a 70 SF / Mowilith LDM 1871 PVC paint

Thickener

Composition (% by weight) TE (% by weight) Time needed to begin dissolution (minutes) Time needed to complete the dissolution (minutes) Qualification of ease of incorporation

NLS 200 commercial

HMPAPE / water / BC (25/60/15) 0.27  10 twenty Hard

TK 53

HMPAPE / water / BTG (20.7 / 62.3 / 17) 0.32  2 9 Moderate

TK 55 Invention

HMPAPE / water / BTG (17.5 / 66.5 / 16) 0.33  one 4 Easy

TK 62 Invention

HMPAPE / water / BTG / Surfynol 465 (17.5 / 66.5 / 13.5 / 2.5) 0.50  one 2 Easy

TK 65 Invention

HMPAPE / water / BTG / Surfynol 465 (20.2 / 60.6 / 13.2 / 6) 0.36  one 4,5 Easy

NLS 210 (same lot as before)

0.24  5 > 20 Hard

NLS 210 + 0.5% by weight of Surfynol 465

0.24  4 18 Hard

NLS 210 + 1% by weight of Surfynol 465

0.24  3 13 Moderate

NLS 210 + 2.5% by weight of Surfynol 465

0.24  2 8 Moderate

NLS 210 + 5% by weight of Surfynol 465

0.24  1.5 4,5 Easy

Table 4

PVC paint formulation 70 Without Solvent Mowilith LDM 1871

Ingredients

Parts by weight

Water

155.0

Calgon N

3.0

Lopon 894

3.0

Shake 315

3.0

Thioxide TR-92

100.0

China-Clay Speswhite

50.0

Annoy 200 P

50.0

Omycarb 2 GU

264.0

Micro Talc WT 1

47.0

Shake 315

1.0

Preventol D7

2.0

Mowilith LDM 1871

158.0

H2O / Polymer

164.0

Total

1000

RAW MATERIAL

FUNCTION CHEMICAL DESCRIPTION SUPPLIER

Calgon N

Wetting agent Sodium polyphosphate BK Giulini Chemie

Lopon 894

Dispersing agent Polyacrylate, sodium salt BK Giulini Chemie

Shake 315

Defoaming Modified Fatty Compounds Münzing Chemie

Thioxide TR-92

Pigment Titanium dioxide Hunstman

China-Clay Speswhite

Load Clay Imerys

Annoy 200 P

Load Clay, calcined Imerys

Omycarb 2 GU

Load CaCO3, average particle size: 2.5 micrometers Omya

Micro. Talc WT 1

Load talcum powder Norwegian Talc

Preventol D7

Preservative Aqueous, formaldehyde free formulation Bayer

Mowilith LDM 1871

Binder Vinyl Acetate-Ethylene Clariant

Claims (47)

one.

An aqueous polymer dispersion comprising: a) hydrophobic modified poly (acetal- or ketal-polyether) (b) water, and c) a viscosity reducing agent chosen from the group consisting of

i) an ethoxylated alcohol having a C9-12 hydrocarbon residue component, ii) an ethoxylated acetylenic diol,   iii) a phosphate ester iv) a combination of ethoxylated alcohol and anionic dialkyl sulphosuccinate, and v) a combination of ethoxylated alcohol and an anionic phosphate ester.

2.

The aqueous dispersion of claim 1, wherein HM-PAPE has an upper limit of weight average molecular weight (Pm) of 100,000.

3.

The aqueous dispersion of claim 1, wherein HM-PAPE has an upper limit of weight average molecular weight (Pm) of 50,000.

Four.

The aqueous dispersion of claim 1, wherein HM-PAPE has an upper limit of weight average molecular weight (Pm) of 40,000.

5.

The aqueous dispersion of claim 1, wherein HM-PAPE has a lower limit of weight average molecular weight (Pm) of 3,000.

6.

The aqueous dispersion of claim 1, wherein HM-PAPE has a lower weight average molecular weight (Pm) limit of 4,000.

7.

The aqueous dispersion of claim 1, wherein HM-PAPE has a lower weight average molecular weight (Pm) limit of 8,000.

8.

The aqueous dispersion of claim 1, wherein HM-PAPE is a hydrophobic terminally protected poly (acetal- or ketal-polyether).

9.

The aqueous dispersion of claim 1, wherein HM-PAPE is a hydrophobic terminally protected poly (acetal- or ketal-polyether) having terminal protection groups as well as pendant hydrophobic groups.

10.

The aqueous dispersion of claim 1, wherein HM-PAPE is a hydrophobically modified poly (acetal- or ketal-polyether) having hydrophobic C3-C30 alkyl groups.

eleven.

The aqueous dispersion of claim 1, wherein HM-PAPE is a hydrophobic terminally protected poly (acetal- or ketal-polyether) having C12-C18 alkyl hydrophobic groups.

12.

The aqueous dispersion of claim 1, wherein HM-PAPE is a hydrophobic terminally protected poly (acetal- or ketal-polyether) having hydrophobic alkylaryl groups.

13.

The aqueous dispersion of claim 1, wherein HM-PAPE is a hydrophobic terminally protected poly (acetal- or ketal-polyether) having hydrophobic methylphenyl groups in its pendant groups.

14.

The aqueous dispersion of claim 1, wherein HM-PAPE is present in an upper limit amount of 40% by weight.

fifteen.

The aqueous dispersion of claim 1, wherein HM-PAPE is present in an upper limit amount of 30% by weight.

16.

The aqueous dispersion of claim 1, wherein HM-PAPE is present in an upper limit amount of 20% by weight.

17.

The aqueous dispersion of claim 1, wherein HM-PAPE is present in a lower limit amount of 10% by weight.

18.

The aqueous dispersion of claim 1, wherein HM-PAPE is present in a lower limit amount of 15% by weight.

19.

The aqueous dispersion of claim 1, wherein the viscosity reducing chemical is present in an upper limit amount of 30% by weight.

twenty.

The aqueous dispersion of claim 1, wherein the viscosity reducing chemical is present in an upper limit amount of 20% by weight.

twenty-one.

The aqueous dispersion of claim 1, wherein the viscosity reducing chemical is present in an upper limit amount of 10% by weight.

22

The aqueous dispersion of claim 1, wherein the viscosity reducing chemical is present in a lower limit amount of 0.5% by weight.

2. 3.

The aqueous dispersion of claim 1, wherein the viscosity reducing chemical is present in a lower limit amount of 1.0% by weight.

24.

The aqueous dispersion of claim 1, wherein the viscosity reducing chemical is present in a lower limit amount of 3.0% by weight.

25.

The aqueous dispersion of claim 1, wherein the water is present in an upper limit amount of 85% by weight.

26.

The aqueous dispersion of claim 1, wherein the water is present in an upper limit amount of 75% by weight.

27.

The aqueous dispersion of claim 1, wherein the water is present in an upper limit amount of 65% by weight.

28.

The aqueous dispersion of claim 1, wherein the water is present in a lower limit amount of 30% by weight.

29.

The aqueous dispersion of claim 1, wherein the water is present in a lower limit amount of 40% by weight.

30

The aqueous dispersion of claim 1, wherein the water is present in a lower limit amount of 50% by weight.

31.

The aqueous dispersion of claim 1, wherein the viscosity reducing agent is 2,4,7,9-tetramethyl5-decin-4,7-diol ethoxylate.

32

The aqueous dispersion of claim 1, wherein the reducing agent is a phosphate ester.

33.

The aqueous dispersion of claim 1, wherein the viscosity reducing chemical is alcohol ethoxylated (C10- (EO) 6).

3. 4.

The aqueous dispersion of claim 1, wherein the viscosity reducing chemical is tetrabutylene glycol monobutyl ether.

35

The aqueous dispersion of claim 1, wherein the viscosity reducing chemical is C9-11 (EO) 6.

36.

The aqueous dispersion of claim 1, wherein butyltriglycol is also present.

37.

An aqueous protective coating composition comprising the dispersion of claim 1.

38.

The aqueous protective coating composition of claim 37, further comprising a latex.

39.

The aqueous protective coating composition of claim 38, wherein the latex is selected from the group consisting of 100% acrylics, vinyl acrylics and styrene acrylics.

40

The aqueous protective coating composition of claim 38, wherein the aqueous protective coating further comprises a pigment.

41.

The aqueous protective coating composition of claim 40, wherein the pigment is selected from the group consisting of hydrated aluminum oxide, barium sulfate, calcium silicate, clay, silica, talc, titanium dioxide, zinc oxide and their mixtures

42

The aqueous protective coating composition of claim 40, wherein the aqueous protective coating has an upper limit volume pigment (PVC) concentration of 85%.

43

The aqueous protective coating composition of claim 40, wherein the aqueous coating

protector has a pigment concentration in volume (PVC) of an upper limit of 75%.

44.

The aqueous protective coating composition of claim 40, wherein the aqueous protective coating has an upper limit volume pigment (PVC) concentration of 65%.

45. The aqueous protective coating composition of claim 40, wherein the aqueous protective coating 5 has a volume pigment concentration (PVC) of a lower limit of 10%.

46.

The aqueous protective coating composition of claim 40, wherein the aqueous protective coating has a volume pigment concentration (PVC) of a lower limit of 20%.

47

A method of incorporating the HM-PAPE polymer into a protective coating formulation that

it comprises adding the aqueous dispersion of claim 1 to the coating formulation while stirring the formulation concurrently.