Phosphate Surfactant Composition

Abstract

A phosphate surfactant composition comprising a phosphate surfactant formed from a secondary alcohol alkoxylate. [Selection diagram] None

Description

[Technical field]

[0001] Embodiments of the present disclosure are directed to phosphate surfactant compositions, and more specifically, embodiments are directed to phosphate surfactant compositions comprising phosphate surfactants formed from secondary alcohol alkoxylates. [Background technology]

[0002] Surfactants can be used in many applications including emulsion polymerization, coatings, agricultural formulations, fragrance emulsions, degreasing, and metal working, among others. The industry continues to focus on developing new and improved surfactants. Summary of the Invention

[0003] The present disclosure provides compounds of formula I: [ka]

[0004] [In the formula, R 1 and R 2 are each independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms, so that R 1 and R 2 The combination of R 3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, n is an integer from 1 to 50, and each M is independently hydrogen, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or a substituted ammonium group;

[0005] Formula II: [ka]

[0006] [In the formula, each R 1 and R 2are independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms, so that R 1 and R 2 and each R 3 are independently hydrogen or an alkyl group containing 1 to 6 carbon atoms, n is an integer from 1 to 50, and M is hydrogen, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or a substituted ammonium group, or a combination thereof.

[0007] The present disclosure provides emulsions formed with phosphate surfactant compositions.

[0008] The present disclosure provides coatings formed with the emulsions disclosed herein.

[0009] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every embodiment of the present disclosure. The following description more particularly illustrates exemplary embodiments. In several places throughout this application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list. [Brief description of the drawings]

[0010] [Figure 1] An image of salt spray resistance is shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Disclosed herein is a phosphate surfactant composition. An embodiment of the disclosure provides that the phosphate surfactant composition is substantially free of alkylphenol ethoxylates.

[0012] Alkylphenol ethoxylates have been used as surfactants in the past, but due to the many issues associated with alkylphenol ethoxylates, including in particular various government regulations, there is an increasing market need for surfactant compositions that are substantially free of alkylphenol ethoxylates.

[0013] As mentioned above, the phosphate surfactant composition disclosed herein is substantially free of alkylphenol ethoxylate.As used herein, "substantially free of alkylphenol ethoxylate" refers to less than 5 weight percent of alkylphenol ethoxylate based on the total weight of the phosphate surfactant composition.For example, the phosphate surfactant composition may contain 0 weight percent of alkylphenol ethoxylate based on the total weight of the phosphate surfactant composition.In other words, the phosphate surfactant composition may not contain alkylphenol ethoxylate.

[0014] The phosphate surfactant composition disclosed herein may have one or more properties that are desirable for various applications.For example, the phosphate surfactant composition disclosed herein may have improved, i.e. reduced, critical micelle concentration compared to other phosphate surfactants.The phosphate surfactant composition disclosed herein may be used in many different applications.

[0015] The critical micelle concentration (CMC) is the concentration of a surfactant above which micelles begin to form. The CMC can be an important property of a surfactant for many applications. For example, the surface tension does not decrease further above the CMC, so in many processes the CMC can be used to specify the limit concentration of the surfactant. Furthermore, in some applications, such as cleaning applications, the CMC can be used as an indicator of the efficiency of the surfactant.

[0016] The phosphate surfactant compositions disclosed herein may have improved, i.e., reduced, foam height compared to other phosphate surfactants. Reduced foam is particularly desirable for many applications, such as latex paints, automatic dishwashing, etc.

[0017] The phosphate surfactant compositions disclosed herein comprise a compound represented by Formula I: [ka]

[0018] [In the formula, R 1 and R 2 are each independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms, so that R 1 and R 2 The combination of R 3 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, n is an integer from 1 to 50, and each M is independently hydrogen, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or a substituted ammonium group.

[0019] All individual values ​​and subranges of 8 to 18 carbon atoms are included, e.g., R 1 and R 2 The combination with may contain as low as 8, 10, or 12 carbon atoms to as high as 18, 16, or 14 carbon atoms. For example, R 1 and R 2 The combination with may contain 8 to 16, 8 to 14, 10 to 18, 10 to 16, 10 to 14, 12 to 18, 12 to 16, or 12 to 14 carbon atoms.

[0020] All individual values ​​and subranges from 1 to 50 are included, for example, n can be an integer from a lower limit of 1, 2, 3, or 4 to an upper limit of 50, 35, 25, or 15.

[0021] The phosphate surfactant compositions disclosed herein comprise a compound represented by Formula II: [ka]

[0022] [In the formula, each R 1 and R 2 are independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms, so that R 1 and R 2 and each R 3 are independently hydrogen or an alkyl group containing 1 to 6 carbon atoms, n is an integer from 1 to 50, and M is hydrogen, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or a substituted ammonium group.

[0023] All individual values ​​and subranges of 8 to 18 carbon atoms are included, e.g., R 1 and R 2 The combination with may contain as low as 8, 10, or 12 carbon atoms to as high as 18, 16, or 14 carbon atoms. For example, R 1 and R 2 The combination with may contain 8 to 16, 8 to 14, 10 to 18, 10 to 16, 10 to 14, 12 to 18, 12 to 16, or 12 to 14 carbon atoms.

[0024] All individual values ​​and subranges from 1 to 50 are included, for example, n can be an integer from a lower limit of 1, 2, 3, or 4 to an upper limit of 50, 35, 25, or 15.

[0025] The phosphate surfactants disclosed herein, i.e., those represented by Formula I and Formula II, can be formed from a secondary alcohol alkoxylate, such as a secondary alcohol ethoxylate. Formula III: [ka]

[0026] [In the formula, R 1 and R 2 are each independently hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms, so that R 1 and R 2 The combination of R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 50.

[0027] All individual values ​​and subranges of 8 to 18 carbon atoms are included, e.g., R 1 and R 2 The combination with may contain as low as 8, 10, or 12 carbon atoms to as high as 18, 16, or 14 carbon atoms. For example, R 1 and R 2 The combination with may contain 8 to 16, 8 to 14, 10 to 18, 10 to 16, 10 to 14, 12 to 18, 12 to 16, or 12 to 14 carbon atoms.

[0028] All individual values ​​and subranges from 1 to 50 are included, for example, n can be an integer from a lower limit of 1, 2, 3, or 4 to an upper limit of 50, 35, 25, or 15.

[0029] The secondary alcohol alkoxylate represented by formula III can be prepared using known equipment, reaction components and reaction conditions.The secondary alcohol alkoxylate represented by formula III can be commercially available.The examples of commercially available secondary alcohol alkoxylate represented by formula III include, but are not limited to, ECOSURF ® LF-30 and ECOSURF ® LF-45 (both available from The Dow Chemical Company), and secondary alcohol ethoxylate TERGITOL ® 15-S-5 and TERGITOL ® 15-S-7 (both available from The Dow Chemical Company).

[0030] The phosphate surfactants represented by formula I and formula II can be formed by a phosphorylation process. For example, in the formation of the phosphate surfactants represented by formula I and formula II, a secondary alcohol alkoxylate represented by formula III is reacted with polyphosphoric acid (H 3 PO 4 ) and phosphorus pentoxide (P 2 O 5 The phosphorylation process may be carried out using known equipment, additional reaction components, and reaction conditions.

[0031] The secondary alcohol alkoxylate represented by formula III can be reacted with polyphosphoric acid at a molar ratio of 5:1 to 1:5 of the moles of secondary alcohol alkoxylate to the moles of polyphosphoric acid. The secondary alcohol alkoxylate represented by formula III can be reacted with phosphorus pentoxide at a molar ratio of 5:1 to 1:5 of the moles of secondary alcohol alkoxylate to the moles of phosphorus pentoxide. The secondary alcohol alkoxylate represented by formula III can be reacted with polyphosphoric acid and phosphorus pentoxide sequentially, i.e., the secondary alcohol alkoxylate can be reacted with polyphosphoric acid and then phosphorus pentoxide is added, or the secondary alcohol alkoxylate can be reacted with phosphorus pentoxide and then polyphosphoric acid is added. The secondary alcohol alkoxylate represented by formula III can be reacted with polyphosphoric acid and phosphorus pentoxide simultaneously, i.e., the secondary alcohol alkoxylate, phosphoric acid, and phosphorus pentoxide can be combined for the phosphorylation process.

[0032] Because a secondary alcohol alkoxylate represented by Formula III is used to form the phosphate surfactant represented by Formula I and Formula II, the phosphate surfactant compositions disclosed herein may include a secondary alcohol alkoxylate represented by Formula III, e.g., an unreacted reactant.

[0033] The phosphate surfactant composition disclosed herein may comprise from 20 to 99.9 weight percent of the phosphate surfactant represented by Formula I, based on the total weight of the phosphate surfactant composition. All individual values ​​and subranges from 20 to 99.9 weight percent are included, for example, the phosphate surfactant composition may comprise a lower limit of 20, 21, 22, 23, 24, 25, 27, 28, or 30 weight percent to an upper limit of 99.9, 95, 90, 85, 80, 75, 70, 65, or 60 weight percent of the phosphate surfactant represented by Formula I, based on the total weight of the phosphate surfactant composition.

[0034] The phosphate surfactant composition disclosed herein may comprise from 0.1 to 80 weight percent of the phosphate surfactant represented by Formula II, based on the total weight of the phosphate surfactant composition, including all individual values ​​and subranges from 0.1 to 80 weight percent, for example, the phosphate surfactant composition may comprise a lower limit of 0.1, 0.3, 0.5, or 1.0 weight percent to an upper limit of 80, 60, 40, or 20 weight percent of the phosphate surfactant composition represented by Formula II, based on the total weight of the phosphate surfactant composition.

[0035] The phosphate surfactant composition disclosed herein may comprise from 0.01 to 10 weight percent of the secondary alcohol alkoxylate represented by formula III, based on the total weight of the phosphate surfactant composition, including all individual values ​​and subranges from 0.01 to 10 weight percent, for example, the phosphate surfactant composition may comprise a lower limit of 0.01, 0.1, or 0.5 weight percent to an upper limit of 10, 7.5, or 5 weight percent of the secondary alcohol alkoxylate represented by formula III, based on the total weight of the phosphate surfactant composition.

[0036] The phosphate surfactant composition disclosed herein may be aqueous or non-aqueous. As used herein, a non-aqueous phosphate surfactant composition refers to a composition having a water concentration of less than 0.1 weight percent based on the total weight of the phosphate surfactant composition. When water is included, the phosphate surfactant composition disclosed herein may contain 0.1 to 80 weight percent water based on the total weight of the phosphate surfactant composition. All individual values ​​and subranges from 0.1 to 80 weight percent are included, for example, the phosphate surfactant composition may contain a lower limit of 0.1, 1, 3, 5, 10, 15, 20, 35, or 40 weight percent water to an upper limit of 80, 77, 75, 72, 70, 65, or 60 weight percent water based on the total weight of the phosphate surfactant composition.

[0037] The phosphate surfactant compositions disclosed herein may be used together with one or more known surfactants. Different amounts of one or more known surfactants may be used for various applications. For example, a phosphate surfactant having the formula: 4 O(AO) z H, wherein R 4 is C 6 ~C 24 and AO is a linear or branched alkyl of the formula 2 ~C 4 Alkylene oxide, z is 1 to 50. 4 O(AO) z The alkyl alkoxylate surfactant having H may be used with the phosphate surfactant composition at 0.01 to 70 weight percent, based on the total weight of the phosphate surfactant composition. All individual values ​​and subranges from 0.01 to 70 weight percent are included, for example, alkyl alkoxylate surfactants having the formula: R 4 O(AO) z Alkyl alkoxylate surfactants having H may be used at lower limits of 0.01, 3.0, or 5.0 weight percent to upper limits of 70, 50, or 30 weight percent, based on the total weight of the phosphate surfactant composition.

[0038] The phosphate surfactant compositions disclosed herein may have a solids content of from 20 to 100 percent by weight, based on the total weight of the phosphate surfactant composition, including all individual values ​​and subranges from 20 to 100 percent by weight, for example, the phosphate surfactant composition may have a solids content of from a lower limit of 20, 25, or 30 percent by weight to an upper limit of 100, 95, or 90 percent by weight, based on the total weight of the phosphate surfactant composition.

[0039] As mentioned, the phosphate surfactant composition disclosed herein may have an improved, i.e., reduced, critical micelle concentration compared to other phosphate surfactants. Reducing the critical micelle concentration is desirable for many applications. The phosphate surfactant composition may have a critical micelle concentration of 50 to 1000 ppm. All individual values ​​and subranges between 50 and 1000 ppm are included, for example, the phosphate surfactant composition may have a critical micelle concentration of a lower limit of 50, 60, 75, 85, 100, 110, 120, 130, 140, 145, 150, or 160 ppm to an upper limit of 1000, 900, 800, 700, 600, 500, 400, 300, 245, 235, 225, or 215 ppm.

[0040] Furthermore, as mentioned, the phosphate surfactant composition disclosed herein may have an improved, i.e., reduced, foam height compared to other phosphate surfactants. Reducing foam height is desirable for many applications. The phosphate surfactant composition may have a foam height of 110-140 mm, determined by the Ross-Miles Foam Height Test according to GB / T-7462-94 at 0.2 wt.% and reported at 0 minutes. All individual values ​​and subranges of 110-140 mm are included, for example, the phosphate surfactant composition may have a foam height of a lower limit of 110, 115, or 120 mm to an upper limit of 140, 138, or 136 mm, determined by the Ross-Miles Foam Height Test according to GB / T-7462-94 at 0.2 wt.% and reported at 0 minutes. The phosphate surfactant composition may have a foam height of 20 to 130 mm, as determined by the Ross-Miles Foam Height Test according to GB / T-7462-94 at 0.2 wt % and reported at 5 minutes. All individual values ​​and subranges from 20 to 130 mm are included, for example, the phosphate surfactant composition may have a foam height of a lower limit of 20, 30, 40, 50, 60, 70, 80, 90, or 95 mm to an upper limit of 130, 128, 127, 125, 123, 122, 121, or 120 mm, as determined by the Ross-Miles Foam Height Test according to GB / T-7462-94 at 0.2 wt % and reported at 5 minutes.

[0041] The phosphate surfactant compositions disclosed herein can be used to form a dispersion, e.g., an emulsion, sometimes referred to as a monomer emulsified in a continuous aqueous phase. The emulsion can be prepared, for example, with the monomer by conventional emulsion polymerization involving known emulsion polymerization ingredients and reaction conditions. Examples of monomers include, but are not limited to, styrene, ethylhexyl acrylate, methacrylic acid, methyl methacrylate, butyl acrylate, acrylamide, acrylic acid, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene, 1-dodecene, hexyl acrylate, octyl acrylate, isooctyl acrylate, n-decyl acrylate, isodecyl acrylate, tert-butyl acrylate, hexyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl acrylate, and combinations thereof, among others. The monomers can be reacted to form homopolymers and / or copolymers. Emulsion polymerization can be carried out using free radical generating initiators, which can be used, for example, in amounts of 0.01 percent to 5 percent based on the total weight of the monomers.

[0042] Optionally, other ingredients known in emulsion polymerization may be used, such as chelating agents, buffers, inorganic salts, and pH adjusters, among others. Varying amounts of ingredients may be used for different applications.

[0043] The emulsions disclosed herein, i.e., emulsions formed with the phosphate surfactant compositions disclosed herein, may have a solids content of 25 to 65 weight percent, based on the total weight of the emulsion, including all individual values ​​and subranges from 25 to 65 weight percent, for example, the emulsions may have a solids content of a lower limit of 25, 30, 35, 37, or 40 weight percent to an upper limit of 65, 63, 60, 58, or 55 weight percent, based on the total weight of the emulsion.

[0044] One or more embodiments of the present disclosure provide that the emulsion has an average particle size of 10 nm to 500 nm, including all individual values ​​and subranges from 10 nm to 500 nm, for example, the emulsion can have an average particle size from a lower limit of 10, 25, or 50 nm to an upper limit of 500, 300, or 150 nm.

[0045] The emulsions formed from the phosphate surfactant compositions disclosed herein can be used to form coatings that can be used in many different coating applications, such as industrial coating applications, architectural coating applications, automotive coating applications, outdoor furniture coating applications, among others.

[0046] Advantageously, the coatings disclosed herein may have one or more properties desirable for various applications. For example, the coatings disclosed herein may have improved color development, e.g., reduced color difference between touched and untouched portions of the coating, as compared to other coatings.

[0047] Additionally, the coatings disclosed herein may have improved gloss, eg, greater than or equal to gloss, as compared to other coatings.

[0048] The coatings disclosed herein, i.e., coatings formed with the emulsions disclosed herein, can be prepared, for example, by conventional coating formation processes that include known coating ingredients and conditions. For example, the coatings can be prepared by combining the emulsion with one or more coating ingredients. Examples of coating ingredients include, but are not limited to, thickeners, fillers, pH adjusters, dispersants, wetting agents, defoamers, colorants, biocides, flow agents, crosslinkers, antioxidants, plasticizers, leveling agents, thixotropic agents, adhesion promoters, and preservatives. Different amounts of one or more coating ingredients can be used for different applications.

[0049] The coating may be applied to one or more surfaces of an article or structure by any method. Such methods include, but are not limited to, spraying, dipping, roll coating, and any other conventional techniques generally known in the art. Surfaces of such structures that are coated with the coating composition may include concrete, wood, metal, plastic, glass, drywall, among others. Known equipment, ingredients, and conditions may be used in applying the coating. The coating may form one or more layers with various thicknesses for different applications. EXAMPLES

[0050] In the examples, various terms and names for materials are used, including, for example:

[0051] TERGITOL(TM) 15-S-5 (Formula III [wherein, R 1 and R 2 and R 3 is hydrogen], available from The Dow Chemical Company), TERGITOL™ 15-S-7 (formula III [wherein R 1 and R 2 and R 3 is hydrogen], available from The Dow Chemical Company), polyphosphoric acid (available from SinoPharma Co. Ltd.), phosphorus pentoxide (available from SinoPharma Co. Ltd.), RHODAFAC® RS-610S25 (phosphate surfactant, sodium phosphate of isotridecyl ethoxylate, available from Solvay).

[0052] The phosphate surfactant composition of Example 1 was formed as follows: TERGITOL™ 15-S-5 (104.8 grams, 0.25 moles) was added under nitrogen to a vessel maintained at 35° C. and constantly stirred. Polyphosphoric acid (15.0 g, 0.175 moles) was gradually added to the contents of the vessel over 30 minutes, the temperature was raised to 45° C., and the contents of the vessel were constantly stirred. Phosphorus pentoxide (5.3 g, 0.075 moles) was added to the contents of the vessel, the temperature was raised to 55° C., and the contents of the vessel were constantly stirred. The temperature was then raised to 80° C., and the contents of the vessel were constantly stirred for about 12 hours. Water (1 milliliter) was added to the contents of the vessel and constantly stirred for about 2 additional hours while the contents of the vessel were maintained at 80° C. The contents of the vessel were then cooled to 65° C., and hydrogen peroxide (1 milliliter) was added to the contents of the vessel. The contents of the vessel were stirred constantly and cooled to about 20° C. in about 30 minutes to provide Example 1. The contents of the vessel were then optionally diluted with water (290 milliliters) and the pH was adjusted to about 7 with sodium hydroxide (1 mol / L). The solids content of Example 1 was about 30 weight percent. Titration analysis of Example 1 indicated that the molar ratio of the phosphate surfactant represented by Formula I to the phosphate surfactant represented by Formula II was about 82:18.

[0053] The phosphate surfactant composition of Example 2 was formed as in Example 1, with the change being that TERGITOL™ 15-S-7 was used instead of TERGITOL™ 15-S-5.

[0054] Comparative Example A was RHODAFAC® RS-610.

[0055] The properties of Example 1, Example 2, and Comparative Example A are reported in Table 1.

[0056] Solids content was determined by weight loss upon drying at 105° C. for 2 hours.

[0057] Appearance was determined by visual inspection.

[0058] Surface tension and critical micelle concentration (CMC) were determined as follows: Surface tension was measured with KRUSS Force Tensiometer K100C. Aqueous solutions of 10000 ppm surfactant as mother solution and water as blank solution were prepared respectively. Surfactant mother solution was gradually added to water in known amounts and the surface tension at different surfactant concentrations was recorded. Surface tension values ​​were plotted against concentration and CMC was determined from the break point of the plot.

[0059] The foam height was determined by the Ross-Miles foam height test. A 0.2 wt% aqueous surfactant solution was prepared, and then the measurement was carried out according to GB / T-7462-94.

[0060] The wetting time was determined as follows: A 0.5 wt% aqueous surfactant solution was prepared, and cotton fabric was cut into circles with the same size (diameter = 35 mm). The wetting time of the cotton fabric in the aqueous surfactant solution was recorded according to GB / T-11983-2008.

[0061] Ca 2+ The stability was determined according to GB / T-7381-2010.

[0062] The alkali resistance was determined according to GB / T-5556-2003. [Table 1]

[0063] The data in Table 1 show that Examples 1 and 2 each have an improved, ie, reduced, critical micelle concentration as compared to Comparative Example A.

[0064] Additionally, the data in Table 1 show that Example 1 and Example 2 each have improved, ie, reduced, foam height as compared to Comparative Example A.

[0065] The emulsion of Example 3 was formed as follows.

[0066] Example 1 (3.2 grams [relative to the solids content of Example 1]), styrene (207.0 grams), 2-ethylhexyl acrylate (170.2 grams), methyl methacrylate (69.0 grams), methacrylic acid (13.8 grams), ammonium bicarbonate (1.38 grams), and water (300 grams) were added to a vessel and stirred at a temperature of about 20° C. for about 30 minutes to form a pre-emulsion mixture.

[0067] Example 1 (2.3 grams [based on the solids of Example 1]) and water (300 grams) were added to a 2 liter jacketed reactor with mechanical stirring and the reactor contents were heated to about 87° C. The pre-emulsion mixture (2 weight percent based on the reactor contents) and aqueous ammonium persulfate solution (1.2 grams of ammonium persulfate in 20 grams of water) were then added to the reactor contents while maintaining the temperature, and the reactor conditions were maintained for about 10 minutes for the seed polymerization. The remaining pre-emulsion mixture and aqueous ammonium persulfate solution (1.8 grams of ammonium persulfate in 36.8 grams of water) were then added dropwise to the reactor contents over a 3 hour period, and one hour after this addition, the reactor conditions were maintained at about 87° C. to allow reaction time for the emulsion polymerization. The reactor contents were then cooled to about 45° C., aqueous ammonia was added to adjust the pH to about 7-8, and the emulsion was then filtered through a 100 mesh cloth filter to provide Example 3.

[0068] The emulsion of Example 4 was formed as in Example 3, with the change that Example 2 was used instead of Example 1.

[0069] The emulsion of Comparative Example B was formed as in Example 3, with the exception that Comparative Example A was used instead of Example 1.

[0070] The properties of Example 3, Example 4, and Comparative Example B are reported in Table 2.

[0071] Solids content was determined by weight loss upon drying at 105° C. for 2 hours.

[0072] The measurement of polymerization residue was carried out as follows: the emulsion was filtered through a 100 mesh filter cloth. The flocculants collected on the cloth filter were washed with tap water, dried at ambient temperature, and weighed. The weight percentage of the dried flocculants relative to the total weight of the emulsion was used as an index of polymerization stability. The lower the percentage of flocculants, the better the polymerization stability.

[0073] The average particle size and its peak width were determined by a zeta potential particle analyzer (Malvern Nano ZS).

[0074] Ca 2+ The stability was determined according to GB / T-20623-2006. [Table 2]

[0075] The coating of Example 5 was formed as follows.

[0076] Deionized water (42 grams), OROTAN™ 681 (7.8 grams, dispersant, available from The Dow Chemical Company), Surfynol TG (2 grams, wetting agent, available from Air Products), aqueous ammonia (2 grams, 28 weight percent ammonia solution), and Tego Airex 902W (0.46 grams, defoamer, available from Evonik) were added to the first vessel and stirred with a dispersing plate at about 400 rpm for 5 minutes, after which Ti-Pure R-706 (209 grams, colorant, titanium dioxide) was added to the contents of the first vessel and the contents were stirred at about 2000 rpm for 25 minutes. Additional deionized water (42 grams) was then added to the contents of the first vessel and the contents were stirred at about 400 rpm for 5 minutes.

[0077] Example 3 (536.6 grams) was added to a second vessel and stirred at approximately 400 rpm, and deionized water (50 grams) and aqueous ammonia (4 grams, 28 weight percent ammonia solution) were added to the contents of the second vessel and the contents were stirred at approximately 400 rpm for 5 minutes.

[0078] The contents of the first vessel were added to the second vessel and stirred at about 400 rpm for 5 minutes. Sodium nitrite solution (8.97 grams, corrosion inhibitor, 15% by weight sodium nitrite in water), ACRYSOL™ RM-8W (2.1 grams, thickener, available from The Dow Chemical Company), UCAR™ Filmer IBT (45.5 grams, aggregate, available from The Dow Chemical Company, equivalent to TEXANOL™ ester alcohol), and deionized water (46 grams) were added to the second vessel and stirred at about 400 rpm for 10 minutes to provide Example 5.

[0079] The coating of Example 6 was formed as in Example 5, with the change that the emulsion of Example 4 was used instead of the emulsion of Example 3.

[0080] The coating of Comparative Example C was formed as in Example 5, with the change that the emulsion of Comparative Example B was used instead of the emulsion of Example 3.

[0081] The salt spray resistance of Example 5, Example 6, and Comparative Example C was determined according to ASTM B117 using a 200 μm coating on a metal plate, respectively. The resulting salt spray resistance images are shown in FIG. 1. Image 102 shows the coating of Example 5 after 24 hours, image 104 shows the coating of Example 6 after 24 hours, image 106 shows the coating of Comparative Example C after 24 hours, image 108 shows the coating of Example 5 after 72 hours, image 110 shows the coating of Example 6 after 72 hours, and image 112 shows the coating of Comparative Example C after 72 hours. As shown in FIG. 1, each of Examples 5 and 6 has improved, i.e., reduced, corrosion resistance compared to Comparative Example C after both 24 hours and 72 hours.

[0082] The gloss at 20°, 60°, and 85° for Example 5, Example 6, and Comparative Example C was determined with a handheld gloss meter (micro-TRI-Gloss from BYK). The results are reported in Table 3. Gloss values ​​that differ by 1.0 or less were considered equivalent, values ​​that differ by more than 1.0 were considered improved, with higher values ​​indicating more desirable gloss. [Table 3]

[0083] The data in Table 3 show that Examples 5 and 6 each have improved, or increased, gloss compared to Comparative Example C at 20°, 60°, and 85°, respectively.

[0084] The emulsion of Example 7 was formed as follows.

[0085] Example 1 (2.7 grams [relative to the solids of Example 1]), styrene (238.0 grams), butyl acrylate (211.0 grams), acrylamide (8.0 grams), acrylic acid (9.5), sodium bicarbonate (0.9 grams), and water (101.0 grams) were added to a vessel and stirred at a temperature of about 20° C. for about 30 minutes to form a pre-emulsion mixture.

[0086] Example 1 (1.2 grams [based on the solids content of Example 1]) and water (283 grams) were added to a 2 liter jacketed reactor with mechanical stirring, and the reactor contents were heated to about 86° C. Thereafter, while maintaining the temperature, an aqueous ammonium persulfate solution (1.2 grams of ammonium persulfate in 8.0 grams of water) was added to the reactor contents, and then the pre-emulsion mixture and an aqueous ammonium persulfate solution (1.8 grams of ammonium persulfate in 88.0 grams of water) were added dropwise to the reactor contents over a period of 3 hours, and one hour after this addition, the reactor conditions were maintained at about 86° C. to allow a reaction time for the emulsion polymerization, after which the reactor contents were cooled to about 65° C., and an aqueous sodium formaldehyde sulfoxylate solution (0.32 grams in 12.0 grams of water) and an aqueous t-butyl hydroperoxide solution (0.45 grams in 8.0 grams of water) were added sequentially to the reactor contents to provide an emulsion. The reactor contents were maintained at 65° C. for 30 minutes, then cooled to about 45° C., aqueous ammonia was added to adjust the pH to about 7-8, and the emulsion was then filtered through a 100 mesh cloth filter to provide the emulsion of Example 7.

[0087] The emulsion of Example 8 was formed as in Example 7, with the change that Example 2 was used instead of Example 1.

[0088] The emulsion of Comparative Example D was formed as in Example 7, with the exception that Comparative Example A was used instead of Example 1.

[0089] The properties of Examples 7, 8, and Comparative Example D are reported in Table 4. The properties were determined as described above. [Table 4]

[0090] The coating of Example 9 was formed as follows.

[0091] Deionized water (260 grams), CELLOSIZE™ QP-30000H (2 grams, thickener, available from The Dow Chemical Company), AMP-95 (2 grams, pH adjuster / dispersant / wetting agent, available from Golden Gate Capital) were added to the vessel while stirring with a dispersing plate at about 450 rpm. OROTAN™ 1288 (4.5 grams, dispersant, available from The Dow Chemical Company), ECOSURF™ BD-109 (1 gram, wetting agent, available from The Dow Chemical Company), FOAMMASTER® NXZ (1 gram, antifoaming agent, available from BASF) were each added to the vessel while stirring at about 450 rpm, and the contents of the vessel were stirred for 10 minutes after addition. Ti-Pure R-706 (40 grams, colorant, titanium dioxide), calcined kaolin (125 grams, filler), talcum powder (100 grams, 100 mesh, filler), and calcium carbonate (225 grams, filler) were then added to the vessel while the agitation was increased to about 1800 rpm and maintained for 30 minutes. One-third of the contents of the vessel was used for Example 9, one-third of the contents of the vessel was used for Example 10, and one-third of the contents of the vessel was used for Comparative Example E.

[0092] Example 7 (95 grams), FOAMMASTER® NXZ (1 gram), UCAR™ Filmer IBT (9 grams, aggregates, available from The Dow Chemical Company, corresponding to TEXANOL® ester alcohol), ACRYSOL™ TT-935 (7 grams, thickener, available from The Dow Chemical Company), ROMICA™ CF-1100 (2 grams, biocide, available from The Dow Chemical Company), BIOBAN™ BPK114 (1 gram, preservative, available from The Dow Chemical Company), and deionized water (113 grams) were added to a vessel and stirred at about 1800 rpm for 10 minutes to provide Example 9.

[0093] The coating of Example 10 was formed as in Example 9, with the change that the emulsion of Example 8 was used instead of the emulsion of Example 7.

[0094] The coating of Comparative Example E was formed as in Example 9, with the exception that the emulsion of Comparative Example D was used instead of the emulsion of Example 8.

[0095] The color development of Example 9, Example 10, and Comparative Example E was determined by rub out testing as follows. Red pigment, blue pigment, and black pigment were mixed with each of Examples 9-10 and Comparative Example E in a weight ratio of 1:50 (pigment:coating), respectively. After stirring, the colored coating was applied to a white board (150 μm layer). Immediately thereafter, the coating was gently wiped evenly in a circular motion with a finger (60 circular wipes in a circle of about 3.5 centimeters in diameter) without touching any part of the colored coating. After the circle was wiped, the coating was kept at about 20° C. for 24 hours. Color development was measured by a Sheen Instruments colorimeter. For color development, ΔE indicates the color difference between the wiped circular portion of the coating and the untouched portion of the coating, with a larger ΔE indicating a larger color difference between the areas. These results are reported in Table 5. [Table 5]

[0096] The data in Table 5 show that Examples 9 and 10 each have improved color development, ie, a lower total ΔE, compared to Comparative Example E.

[0097] The 20°, 60°, and 85° gloss of Example 9, Example 10, and Comparative Example E was determined with a handheld gloss meter (micro-TRI-Gloss from BYK). The results are reported in Table 6. Gloss values ​​that differ by 1.0 or less were considered equivalent, values ​​that differ by more than 1.0 were considered improved, with higher values ​​indicating more desirable gloss. [Table 6]

[0098] The data in Table 56 shows that Examples 9 and 10 each have comparable gloss levels compared to Comparative Example E at 20°, 60°, and 85°, respectively.

Claims

1. Formula I: 【Chemistry 1】 [In the formula, R １ and R ２ are each independently hydrogen or a linear or branched alkyl group; R １ and R ２ and the combination R ３ is hydrogen, n is an integer from 5 to 7, and each M is independently hydrogen, an ammonium group, or a substituted ammonium group; Formula II: 【Chemistry 2】 [In the formula, each R １ and R ２ are independently hydrogen or a linear or branched alkyl group, and R １ and R ２ and each R ３ is hydrogen, n is an integer from 5 to 7, and M is hydrogen, an ammonium group, or a substituted ammonium group; Formula III: 【Chemistry 3】 [In the formula, R １ and R ２ are each independently hydrogen or a linear or branched alkyl group; R １ and R ２ and the combination R ３ is hydrogen and n is an integer from 5 to 7; A phosphate surfactant composition comprising from 20 to 99.9 weight percent of the phosphate surfactant represented by formula I, from 0.1 to 80 weight percent of the phosphate surfactant represented by formula II, and from 0.01 to 10 weight percent of the alcohol alkoxylate represented by formula III, based on the total weight of the phosphate surfactant composition.

2. 10. An emulsion formed from the phosphate surfactant composition of claim 1.

3. 3. The emulsion of claim 2, wherein the emulsion has a solids content of from 25 percent to 65 percent by weight, based on the total weight of the emulsion.

4. A coating formed from the emulsion of claim 3.

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