TECHNICAL DATA SHEET TDS-123 Use of Noverite Polyacrylates In Soap, Detergent and Cleaning Products INTRODUCTION A complete detergent product removes soil, controls water hardness and prevents soil and water hardness salts from depositing onto the cleaned articles and washing equipment parts. Noverite polyacrylates assist the surfactant and common detergent builders in detergent formulations in performing all these detergency functions. Polyacrylates are used in many modern detergent formulations as an important detergent ingredient. Noverite polyacrylates are water soluble, multi-functional polyelectrolytes which exhibit a variety of beneficial features useful in powder or liquid laundry and dishwash detergents both in consumer and institutional cleaning products. Noverite polyacrylates: disperse particulate soil. build-up strong electrostatic cleaning forces between the soil particles and the surfaces to be cleaned. sequester calcium, magnesium, iron and other metals. act as excellent scale inhibitors. exhibit detergent and soap building characteristics. aid in detergent and soap processing. are completely water soluble. are available in a wide range of molecular weights. are thermally stable. are hydrolytically stable. are compatible with non-aqueous polar solvents used in liquid detergents. are colorless and odorless. are available in liquid or powder, acid or neutralized forms. Because of their multi-functionality, Noverite polyacrylates are cost-effective ingredients in soap and detergent formulations. The use of these polymers leads to highly desirable end-use effects such as improved detergency, anti-redeposition, lime soap dispersancy, anti-encrustation, iron sequestration and anti-spotting. In the following sections, laboratory data illustrating the performance of Noverite polyacrylates are included. Lubrizol Advanced Materials, Inc. / 9911 Brecksville Road, Cleveland, Ohio 44141-3247 / TEL: 800.379.5389 or 216.447.5000 combination with other substances or in the User s process. Due to variations in methods, conditions and equipment used commercially in processing these materials, no warranties or guarantees are made as to the suitability of the information or products for the applications disclosed. Lubrizol shall not be liable and the User assumes all risk and responsibility for any use or handling of any material beyond Lubrizol's direct control. LUBRIZOL MAKES NO WARRANTIES, EPRESS The information contained herein is being furnished for informational purposes only, upon the express condition that the User makes its own assessment of the appropriate use of such information. While the information contained herein is believed to be reliable, no representations, guarantees or warranties of any kind are made as to its accuracy, suitability for a particular application or the results to be obtained herefrom. Lubrizol Advanced Materials, Inc. ("Lubrizol") cannot guarantee how any products associated with this information will perform in Lubrizol Advanced Materials, Inc. is a wholly owned subsidiary of The Lubrizol Corporation Copyright 2012 / The Lubrizol Corporation OR IMPLIED, INCLUDING, BUT NOT LIMITED TO, For further information, please visit: www.lubrizol.com/homecare THE IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. It is the User s sole responsibility to determine if there are any issues relating to patent infringement of any component or combination of components relating to the supplied information. Nothing contained herein is to be considered as permission, recommendation, nor as an inducement to practice any patented invention without permission of the patent owner.
2 PHYSICAL PROPERTIES Noverite polyacrylates are low to medium molecular weight water solutions of polyacrylic acid. The polymers are also available in sodium salt, dry or liquid forms. The chemical structure of polyacrylic acid is: Currently, n(degree of polymerization) for Noverite polyacrylates ranges from about 10 to 7000, depending upon the polymer selected. Noverite polyacrylates are true polyelectrolytes because they bear multiple charges enabling them to adsorb at interfaces and act as dispersants and threshold inhibiting agents, and because carboxyl groups are present on the backbone which enable them to act as heavy metal ion chelating agents. As a result, these anionic polyelectrolytes act as dispersants and threshold inhibitors. Physical properties for some Noverite polyacrylates, water solutions and dry forms, are listed in Tables 1 and 2, respectively. Noverite polyacrylates are compatible with most commonly used detergent components. The presence of cationic materials may cause precipitation, however. Specific compatibility is discussed in the Compatibility Tests section.
3 3 TABLE 1 TYPICAL PROPERTIES OF NOVERITE K-700 POLYACRYLATES WATER SOLUTIONS Noverite Polymers K-702 K-732 K-752 K-7058 Appearance Hazy to Clear Amber Solution Hazy to Clear Amber Solution Hazy to Clear Amber Solution White/Amber Slightly Hazy Solution Molecular weight* 345,000 5,100 2,100 7,300 Total solids, % 25 50 63 50 Sodium ion content, % -- 0.5 0.8 -- ph (as shipped) 2.2-3.0 2.2-3.0 2.2-3.0 2.2-3.0 ph (1% aqueous solution) 3.0 3.0 3.0 -- Percent neutralization -- 3.4 4.9 -- (weight %) Specific gravity, g/cc 1.09 1.18 1.23 1.23 Viscosity, mpa s at 25 C 400-1200 250-500 400-1400 300-700 TABLE 1 TYPICAL PROPERTIES OF NOVERITE K-700 POLYACRYLATES WATER SOLUTIONS Noverite Polymers K-7058N K-7600N Appearance Clear Amber Solution White/Amber Slightly Hazy Solution Molecular weight* 7,300 120,000 Total solids, % 45 34 Sodium ion content, % 10.5 8.6 ph (as shipped) 5.5-6.5 7.5-9.0 ph (1% aqueous solution) 9.0 10.0 Percent neutralization 90-100 90-100 (weight %) Specific gravity, g/cc 1.30 1.24 Viscosity, mpa s at 25 C 500-3500 1400-3400 * Weight average molecular weight as determined by Gel Permeation Chromatography.
4 4 TABLE 2 TYPICAL PROPERTIES OF NOVERITE K-700 SODIUM POLYACRYLATES - DRY Noverite Polymers K-739 K-759 K-7058D Appearance White Free Flowing Powder White Free Flowing Powder Off-White Free Flowing Powder Moisture content, % 8-14 8-14 8-14 Molecular Weight* 5,100 2,100 7,300 ph (1% aqueous solution) 6.0-9.0 6.0-9.0 6.0-9.0 Percent neutralization 90-100 90-100 90-100 Sodium ion content, % 18.9 17.5 18.0 Bulk density, lbs./ft. 3 37.6 38.2 32.8 * Weight average molecular weight as determined by Gel Permeation Chromatograph.
5 SOAP AND DETERGENT APPLICATIONS In consumer or institutional cleaning, diverse types of soap and detergent products are used for the detergency benefits they provide in the cleaning of fabrics, dishes, metals, floors and other surfaces. Detergency is the wash benefit arising from soil removal, stabilization of the soil in the wash liquor and prevention of soil re-deposition. Soil is a complex mixture of particulate and oily soiling materials such as sweat sebum, street dirt, household soil, occupational soils and deposits of insoluble calcium/magnesium salts normally present in wash water. The specific roles of Noverite polyacrylates are discussed in the following sections: Functional Tests Formulation Tests Compatibility Tests Physical Tests show individual specific performances of polymers when used by themselves. involve performance testing of total cleaning systems with and without polymer. evaluate the interactions of polymers with other components of cleaning systems. present information useful to the formulator. This comprehensive testing program identifies several key end-use functions of Noverite polyacrylates: General dispersancy Lime soap dispersancy Anti-encrustation, anti-scaling and anti-spotting Sequestration Soil removal and suspension Processing aid FUNCTIONAL TESTS Dispersancy Noverite polyacrylates aid in removing particulate soils from articles to be cleaned and keep the soils dispersed and suspended in the water so that they may be easily discarded with the used wash water. Particulates from scale-forming insoluble calcium salts and lime soaps are also dispersed and suspended to facilitate their removal.
6 Particulate Soil Dispersions The adsorption of Noverite polyacrylates onto soil particles aid in the breaking down of large (50-100 microns) soil agglomerates into much smaller (10 microns and below) particles. These particles then remain as stable dispersions to be discarded in a normal rinse cycle during a standard washing operation. Figure 1 illustrates some examples of median particle sizes (in microns) of several types of common particulate soils, in the presence of (dispersed) and in the absence of (undispersed) Noverite polyacrylates. The median particle sizes were determined at 25 ph 8.0 using an Andreason Sedimentation Pipette at varying Noverite polyacrylate concentrations. Figure 1: Dispersion of Particulate Soils 140 No Polymer Noverite K-732 120 Median Particle Size (microns) 100 80 60 40 20 0 Kaolin Clay Iron Oxide Calcium Carbonate Lime Soap Dispersancy Lime soaps are insoluble calcium salts of long chain fatty acids and are among the most difficult laundry soils to remove. Noverite polyacrylates are excellent lime soap dispersants. In soap products, the use of Noverite polyacrylates leads to enhanced quality and quantity of soap lather and prevention of unsightly rings in bathtubs and wash basins especially in hard water areas. Their use in detergent formulations results in the prevention of lime soap deposits on washed clothes. Therefore, whites stay white longer and rancid fatty odors are eliminated.
7 Relative lime soap dispersancy indices for commonly used detergent lime soap dispersants are highlighted in Table 3. Table 3 Relative Lime Soap Dispersing Power (LSDP)* Common Detergent Ingredient LSDP LAS 3.3 STPP 11.1 NTA 7.1 Noverite Polyacrylate 1.8-6.7 * Lime Soap Dispersing Power is the minimum amount of lime soap dispersing agent necessary to completely disperse a known amount of a calcium soap (lime soap). Anti-Encrustation of Fabrics and Anti-Scaling of Washing Equipment Undesirable deposits of insoluble inorganic salts of hardness ions are sometime found on both washed items and metal parts of washing equipment. This can especially be a problem when using low or zero-phosphate and multi-surfactant detergent products. The build-up of these deposits will ultimately lead to poorer detergency and increased fabric harshening. Low molecular weight Noverite polyacrylates, (K-732 and K-752), have been used as scale inhibitors in water treatment applications for the past 20-30 years. They help prevent such deposits on washed goods and washing equipment parts. Noverite K-7058N will also prevent such deposits through a crystal growth inhibition mechanism. Sequestration Calcium & Magnesium A sequestrant builder is incorporated in an anionic detergent product formulation for the specific purpose of preventing the loss of anionic surfactant through precipitation as its insoluble calcium salt. The free calcium ion concentration at which this surfactant loss begins is determined by the solubility product (Ksp) of Ca (LAS) 2, or Ca (SDS) 3, and averages about 5 x 10-5 moles/liter of hardness ion or 5 ppm as CaCO 3. Noverite polyacrylates are effective calcium and magnesium ion sequestrants and can be used to partly replace STPP in low or zero-phosphate detergents. They can also be used synergistically with other low cost builders like zeolite and sodium citrate to obtain better protection for the anionic surfactant in a total detergent formulation. The use of Noverite polyacrylates (2-10%) in detergents provides for flexibility in low or zerophosphate detergent formulations, sometimes with considerable cost savings.
8 The Ca/Mg sequestration capabilities of Noverite polyacrylates (above M w = 10,000) are illustrated in Figure 2. Figure 2: Builder Sequestration Curve 100 Noverite K-7600N Citrate Zeolite Carbonate STPP Free Hardness (ppm) 10 1 0.1 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 Builder Concentration (%) FORMULATION TEST DATA Soil Removal And Soil Stabilization Noverite polyacrylates possess outstanding soil removal and soil stabilization properties by building strong electrostatic repulsive forces between soil particles and the surfaces to be cleaned. Figure 3 shows that when used at 1/5th the level of common detergent polyelectrolytes (e.g., STPP), Noverite K-7600N polyacrylate exhibit excellent detergency and anti-redeposition characteristics. Use conditions 200 ppm CaCO 3 (Ca/Mg = 2) Permanent Hardness 100 ppm CaCO 3 (NaHCO 3 ) Temporary Hardness 130 F, 10 minutes Test-Fabric WFK-10C (clay soil) ph 11.0, detergent dosage 0.2%
9 Figure 3: Terg-o-tometer Detergency 100 90 80 Noverite STPP K-7600N A 5 0 B 30 0 C 5 5 70 % Detergency 60 50 40 30 20 10 0 A B C Process Aid Because of their adsorption characteristics, the high molecular weight Noverite polyacrylate (K- 7600N) has the following potentials for several soap and detergent process aid applications: Improved slurry stability in 40-70 weight percent total solids detergent slurries. Improved binding of spray dried or agglomerated compound detergent particles (reduction of fines ). Improved powder flow characteristics in pneumatic powder transport equipment used in detergent manufacturing. Improved powder anti-caking in large volume storage bins and silos and small volume packages and dispensers. COMPATIBILITY TEST DATA Compatibility testing is carried out to ensure that use of Noverite polyacrylates does not adversely affect the detergent product form, detergent processing method, bleach stability, enzyme stability, etc. Tests to date do not show any negative compatibility effects in soap and detergent formulations. Some of the more pertinent compatibility data is discussed in the following sections.
10 Bleach Stability The inclusion of 3 weight percent of Noverite polyacrylates in a highly alkaline liquid cleaning product does not have any effect on the available chlorine content of the product. Figures 4 and 5 illustrate storage stability results for Noverite K-7058N in a simulated highly alkaline liquid detergent composition initially containing 5 weight percent sodium hypochlorite. Similar satisfactory storage stability data were obtained for Noverite K-7600N polymer. Figure 4: Chlorine Stability @ 50C 110 50 C Control 50 C K-7058N 100 90 80 % Available Chlorine 70 60 50 40 30 20 10 0 0 1 2 3 4 5 6 7 8 Days Storage Figure 5: Chlorine Stability @ 25C 110 25 C Control 25 C K-7058N 100 90 80 % Available Chlorine 70 60 50 40 30 20 10 0 0 20 40 60 80 100 120 140 160 180 Days Storage
11 COMPATIBILITY WITH NON-AQUEOUS SOLVENTS Organic solvents are sometimes used in liquid cleaning, pre-spotting and dishwashing compounds. Table 4 indicates that Noverite polyacrylates are compatible with most nonaqueous solvents commonly used in liquid cleaning and liquid dishwashing compositions. Ordinary solvent concentrations (5-10%) at ph 9.0 were used. Table 4 Solvent Compatibility Ethanol n-propanol Iso-Propanol I-butanol n-amyl Alcohol** Ethylene Glycol Propylene Glycol Cellosolve* Glycerol Sorbitol Compatible Partially Compatible Incompatible * Ethylene glycol monomethyl ether. ** Partly immiscible with water even in the absence of the polymer C Compatible; P Partially Compatible; I Incompatible PHYSICAL TESTS Thermal Stability Experimental polyacrylates, similar in composition and molecular weight to Noverite polyacrylates, have been shown to be thermally stable under simulated boiler conditions.* At 250 C (482 F) for 18 hours at ph 10.5, the polymer exhibits minimal chain scission, decarboxylation and loss of scale inhibition. Noverite K-700 polyacrylates can be expected to remain stable during normal processing operations such as spray drying, agglomerating and blending. (*W.F. Masler, 43rd International Water Conference, Pittsburgh, Oct., 1982) Hydrolytic Stability Noverite polyacrylates are hydrolytically stable over extended periods of time in highly alkaline (ph 13.0) liquid cleaning products. This extraordinary alkali resistance is due to the absence of labile hydrolyzable functional groups in the molecular structure.
12 ENVIRONMENTAL SAFETY Toxicity Animal studies have been conducted to evaluate the acute and aquatic toxicity of the Noverite polyacrylates. These products have undergone varying degrees of testing the results of which suggests that they are practically non-toxic as a result of acute exposure. Some mild irritation of the eye or skin may be expected for those products which do not have a neutral ph. Aquatic toxicity studies using Noverite K-732 polyacrylate indicate the no-effect levels in daphnia and rainbow trout are 10 ppm and 240 ppm, respectively. Similar studies with bluegill also suggest the no-effect level is similar to that for rainbow trout. These data indicated the aquatic toxicity of Noverite K-732 is of a low order of magnitude. Because of the similarity of other Noverite polyacrylates, their aquatic toxicity is not expected to vary greatly from that of Noverite K- 732. In general, the toxicity of polymers decreases as molecular weight increases. Wasteload Effects The Biochemical Oxygen Demand (BOD) and Chemical Oxygen Demand (COD) of Noverite 732 and K-752 polyacrylates have been evaluated. Testing at a concentration of 500 mg/l indicates that the five-day BOD (BOD 5 ) of Noverite K-732 is less than 1 mg/l and the BOD 5 of Noverite K- 752 is 10 mg/l. Laboratory testing of Noverite K-732 and K-752 showed that both of these materials had CODs of 1.78 mg O 2 per mg of Noverite polyacrylate. The above data indicate that these materials are relatively inert.