Ingredients for Home Care Applications Ingredients for Home Care Applications TABLE OF CONTENTS 5 Formulation 1 6 Environmental data Introduction DEQUEST® PB Inulin derivatives find their use as: 1 Introduction • Co-builder • Synergetic boosters for stain removal in combination The Italmatch Chemicals S.p.A. DEQUEST® products offer a unique set of ingredients for household care 2 Nomenclature 6.1. Environmental profile of DEQUEST® phosphonates products. DEQUEST® range includes phosphonates and carboxymetyl inulin derivatives. 3 Chemical and physical properties of DEQUEST® phosphonates and DEQUEST® PB products 6.2. Environmental profile of DEQUEST® PB 6.2.1. Eco-toxicity of DEQUEST® PB More than 40 years ago, DEQUEST® pioneered the 6.2.2. Biodegradability of DEQUEST® PB development of phosphonate based antiscalants. 6.2.3. Other environmental aspects DEQUEST® phosphonates have been the product of 3.1 Summary tables stabilization, 7 Handling 8 Quality of DEQUEST products 3.2.2 Peroxide and bleach stabilization 3.2.3 Enzyme compatibility 3.3 Scale inhibition 3.4 Dispersion / Deflocculation 3.5 Solubility 3.6 Hydrolitic and thermal stability 4 DEQUEST® in Home Care applications 4.1 Laundry 4.1.1. Powder detergent chelation and metal corrosion inhibition in various applications for many years. 3.2 Sequestration 3.2.1 Stability constant choice for scale prevention, dispersion, bleach ® Recently, carboxymethyl inulin has been added to the DEQUEST® line up in order to offer a biodegradable scale inhibitor/dispersant derived from natural source (chicory root). The application fields of DEQUEST ® phosphonates are derived from the following physical and chemical properties: • Strong sequestration of heavy transition metal ions • Strong scale inhibition of phosphate, carbonate and sulphate scales • Dispersion and deflocculation of solids and lipids soils DEQUEST® PB Inulin derivatives demonstrate their benefits owing to: cost effectiveness When the formulation must comply with some environmental standard typically not met by regular detergents raw materials. DEQUEST® products can be easily formulated in liquid, powder, granulated and tablet types of detergents. They can be incorporated by spray-drying, spray-mixing, dryblending or straight mixing of liquids. Their solubility in water is high and they show excellent compatibility with other detergent ingredients. The high purity of the DEQUEST® phosphonates means that customers obtain maximum performance. Performance is shown to be directly related to purity. Italmatch Chemicals S.p.A.’s DEQUEST® range has been the world’s leader in phosphonates for more than 40 years and it is recognized as setting the quality standard in the market. Our long manufacturing experience and stringent process controls ensure our customers receive a consistent quality product that does not vary from shipment to and assistance to customers on formulation and processing of DEQUEST® phosphonates with these properties has led to their 4.2. Dishwashing • dispersant (anti-redeposition) Italmatch Chemicals S.p.A. can provide technical service • Attractive environmental profile excellent • glass corrosion inhibitor As a major supplier of material to the detergent industry, • Scale inhibition and dispersion properties The • Anti-incrustation additives shipment. • Excellent calcium tolerance 4.1.2. Liquid detergent 4.1.3. Laundry additives with DEQUEST® phosphonates of phosphonates and Inulin derivatives in detergents and cleaners. widespread use in detergents or cleaners, DEQUEST® phosphonates can be formulated to promote: 4.3. Hard surface cleaning • Scale inhibition of insoluble salts (Anti-incrustation) • Stabilization of bleaching agents, in particular peracids and activators • Deflocculation • Specific stain removal 2 3 Ingredients for Home Care Applications 3 Chemical and physical properties of DEQUEST® phosphonates and carboxymethyl Inulin based products 2 Nomenclature 2.1 – Phosphonates 2.2 – Carboxymethyl Inulin 3.1 - Summary tables DEQUEST DEQUEST PB are derived from Inulin, a natural substance DEQUEST® 2010/2016/2016D/2016DG phosphonates ® phosphonates are divided into amino- phosphonates and non-amino phosphonates. ® extracted from chicory. Each fructose and the terminal glucose unit carry 3 reactive groups, which can be Chemical name: Table 1 shows the various grades of amino phosphonates; substituted into carboxymethyl groups; practically, 3 1-Hydroxymethylene (1.1 diphosphonic acid) (HEDP) table 2 shows the various grades of non-amino degrees of substitution are produced: 1.5, 2.0 and 2.5 Chemical structure: phosphonates. They are sold as liquid or free-flowing powders and/or granules. These liquids or solid grades can be obtained as acids or salts, which offer application in liquid and powder detergents and cleaners. TABLE 1: DEQUEST® AMINO-PHOSPHONATES Amino backbone DEQUEST® series TABLE 3: DEQUEST CARBOXYMETHYL INULIN ® Average substitution degree per fructose unit (DS) DEQUEST® PB series 1.5 DEQUEST® PB 11615 2 DEQUEST PB 11620 2.5 DEQUEST® PB 11625 HO OH OH P C P O CH3 O DEQUEST® 2000 Ethylenediamine DEQUEST® 2040 Hexamethylenediamine DEQUEST® 2050 Product Diethylenediamine DEQUEST 2060 Product form Acid solution Appearance DEQUEST series DEQUEST® 2010 2-Phosphono 1,2,4-butanetricarboxylic acid DEQUEST® 7000 Chemical properties 1-Hydroxyethylene (1,1-diphosphonic acid) Physical properties Chemical type TABLE 4: DEQUEST® 2010 SERIES ® ® OH ® Ammonia TABLE 2: DEQUEST® NON-AMINO PHOSPHONATES 4 OH DEQUEST® 2010 DEQUEST® 2016 DEQUEST® 2016D DEQUEST® 2016 DG HEDP Na4HEDP Na4HEDP Na4HEDP Clear to pale yellow aqueous solution Tetrasodium salt solution Clear to pale yellow aqueous solution Tetrasodium salt powder White free flowing powder Tetrasodium salt granule White free flowing granule Molecular weight 206 294 294 294 Mean particle size [µ] N.A. N.A. 100 min 400-800 Specific gravity @ 20ºC 1.45 1.31 0.65-0.95 g/cm³ (bulk density) 0.65-1.0 g/cm³ (bulk density) Freezing point [ºC] -25 Active content 60 % as acid pH (1% @ 25ºC) DEQUEST® 2016 should be maintained above +5ºC at all time 21% as acid 30% as salt N.A. N.A. 59% as acid 84% as salt 59% as acid 2.0 max 10-12 11-12 11-12 Chloride [%] <0.1 - - - Iron [ppm Fe] <20 <20 <20 <35 Moisture [%] N.A. N.A. 6-10 13 max 5 Ingredients for Home Care Applications DEQUEST® 2046 / 2047 phosphonates DEQUEST® 2060S / 2066 / 2066A / 2066C2 / 4066 phosphonates Chemical name: ethylenediaminetetra (methylphosphonic acid) Chemical name: (EDTMPA) Diethylenediaminepenta (methyl­phosphonic acid) (DTPMPA) Chemical structure: Chemical structure: O O HO HO OH CH2P PCH2 HO N(CH2) 2N HO CH2P HO DEQUEST® 2047 Na5EDTMPA Na3Ca2,5EDTMPA Product form Pentasodium salt solution Sodium/Calcium salt powder Appearance Clear to pale yellow aqueous solution Off-white free flowing powder Molecular weight 546 597 Mean particle size [µ] N.A. 100 min Specific gravity @ 20ºC 1.32 475-900 kg/m³ (bulk density) Freezing point [ºC] -14 NA Active content 25% as acid 31% as salt 32-36% as acid pH (1% @ 25ºC) 6-8 11-13 Chloride [%] <5 17-20 Iron [ppm Fe] <20 <20 Moisture [%] N.A. 14-17.5 Physical properties Chemical properties DEQUEST 2047 can also be supplied as granule ® 6 O OH OH TABLE 6: DEQUEST® 2060 SERIES DEQUEST® 2060S DEQUEST® 2066A DEQUEST® 2066 DEQUEST® 2066C2 DEQUEST® 4066 DTPMPA DTPMPA.PN Na7DTPMPA Na7DTPMPA Na7DTPMPA Product form Acid solution Partly neutralized sodium salt solution Heptasodium salt solution Appearance Clear, brown aqueous solution Clear, dark amber aqueous solution Clear amber aqueous solution Concentrated heptasodium salt solution Clear amber aqueous solution Molecular weight 573 ~617 727 727 727 Mean particle size [µ] N.A. N.A. N.A. N.A. 150 min Specific gravity @ 20ºC 1.42 1.41 1.29 1.40 600-800 kg/m³ (bulk density) Freezing point [ºC] -25 -20 -14 <-15 N.A. Active content 50% as acid 47% as acid 25% as acid 32% as salt 32% as acid 22% as acid pH (1% @ 25ºC) <2 2-3 6-8 6-8 6-8 Chloride [%] <5 <5 <5 <5 <5 Iron [ppm Fe] <20 <20 <20 <20 <20 Moisture [%] N.A. N.A. N.A. N.A. 4-6 Product Physical properties DEQUEST® 2046 Chemical properties TABLE 5: DEQUEST® 2040 SERIES Product OH P HO OH O CH2 PCH2 CH2P HO NCH2CH2NCH2CH2N HO OH PCH2 OH O O HO OH CH2P PCH2 OH O O O Heptasodium salt proprietary granule Off-white granule 7 Ingredients for Home Care Applications DEQUEST® PB Carboxymethyl Inulin 3.2 – Sequestration Three DEQUEST® PB grades are commercially available as 3.2.1 – Stability constants carboxymethyl inulin solutions with carboxymethylation They are presented as indicative, since these data come degree ranging from 1.5 to 2.5. Additional grades are from different sources and are not obtained under the available upon request. same experimental conditions. Chemical name: sodium carboxymethyl inulin (NaCMI) In practical situations, these values can possibly be helpful to rationalize observations, but are of limited use when it Chemical structure: comes to quantitative prediction of actual effects. CH2OH O TABLE 8: STABILITY CONSTANT LOGARITHM OF SELECTED DEQUEST® PHOSPHONATES, DEQUEST® PB AND OTHER OH CHELANTS. HO Ca++ Mg++ Fe++ Cu++ Zn++ 7.1 4.8 16.21 12.6 10.6 EDTMPA (DEQUEST® 2040) 10.2 9.3 21.7 18.3 DTPMPA (DEQUEST® 2060) 10.7 10.8 25.3 20.1 12.7 10.4 9.8 9.7 HO HOCH2 O O HEDP (DEQUEST® 2010) OH OCH2CO2Na + CH2OCH2CO2Na + CH2 O n O CMI (DEQUEST® PB) 5.0 – 6.0 OH OH CH2OH TABLE 7: DEQUEST® PB SERIES DEQUEST® PB 11615 DEQUEST® PB 11620 DEQUEST® PB 11625 NaCMI NaCMI NaCMI Product form Sodium salt solution Sodium salt solution Sodium salt solution Appearance Brown liquid Brown liquid Brown liquid Molecular weight ~2000 ~2000 ~2000 Specific gravity @ 20ºC 1.2-1.3 1.2-1.3 1.2-1.3 Dynamic viscosity (mP.s @ 20°C) ~25 ~10 ~7 Active content 25 % min as sodium salt 20 % min as sodium salt 15 % min as sodium salt Carboxymethylation degree 1.5 2 2.5 pH @ 25ºC 7-10 7-10 7-10 Chloride [%] 8 max 8 max 10 max Chemical properties Physical properties Product 8 Three “light colour” grades of DEQUEST® PB are also available for formulations where dark colour is not suited. These are DEQUEST® PB 11615D, 11620D and 11625D. NTA 6.4 5.5 STPP 5.2 5.5 Citric Acid 3.5 2.8 11.8 6.1 4.5 EDTA 10.7 8.8 25.0 18.8 16.5 15.8 DEQUEST® phosphonates show on average high chelation power for transition metals and higher values than STPP, NTA or citric acid when it comes to Alkaline Earth ion chelation. The high chelation constants for transition metals make DEQUEST® phosphonates ideal for peroxide bleach stabilization. Moreover, phosphonates are stable in oxygenated bleach environment, unlike the aminocarboxylates, EDTA and NTA which loose their chelation power under these conditions (see the section peroxide and bleach stabilization). 9 Ingredients for Home Care Applications 3.2.2 – Peroxide and bleach stabilization 3.2.3 – Enzyme compatibility On the other hand, DEQUEST® PB exhibits good 3.5.2 - Sodium salts Heavy metal compounds of elements such as iron, Although chelant might have a detrimental effect on the effectiveness at molar ratio between 0.005 and 0.015 In general, solubility constants of DEQUEST® 2046 and manganese and copper catalyze the decomposition of efficiency of enzyme contained in detergent, the DEQUEST® depending on the degree of substitution. 2066 sodium salts diminish with increasing pH and hydrogen peroxide and bleach system. To prevent this 2060 and DEQUEST decomposition, the control of heavy metals is required. efficiency. Furthermore, none of the standard DEQUEST® DEQUEST grades have shown a negative influence on the new generation ® phosphonates are excellent chelants which offer excellent stabilization of bleach systems during the of amylase (Stainzyme 121). FIGURE 1: SHELF LIFE STABILIZATION OF PERBORATE/TAED SYSTEM -ACTIVATED P.FREE DETERGENT RT – STABILIZER FIGURE 3: ENZYME STABILITY - INFLUENCE OF THE CHELANT THE ENZYMATIC STAIN REMOVAL PERFORMANCE AFTER 22 WEEKS OF STORAGE AT RT DEQUEST® 2066 AT 0.5% AS ACTIVE ACID. Stain Removal 90 80 with other anti-redeposition agents contribute to the antigreying effect, or the build-up of dingy soil. No Enzyme sedimentation of kaolin clay (a major soil ingredient) in a No chelant PB 12625D graduated Imhoff cone. In the experiments, 1 g/l of kaolin 40 30 DQ 2016 20 DQ 2066C2 10 60 0 was dispersed in tap water with a calcium hardness of 150 ppm adjusted at pH 10 with NaOH and in the presence of 0.15 % of the dispersant “as is”. Initials 30 DEQUEST® 2066 40 50 Days Blank DISPERSION AT pH 10. 3.3 – Scale inhibition DEQUEST® phosphonates and DEQUEST® PB are effective scale inhibitors. Unlike other chelants, DEQUEST® products FIGURE 2: PERBORATE/TAED STABILISATION 700 ppm have the ability to inhibit scale formation at PERBORATE, 300 ppm TAED, 35 ppm STABILISER, 2 ppm sub-stoechiometric level (Figure 4). Accordingly, they are FE, pH 10, 40 C cost effective scale inhibitor. The scale inhibition at substoechiometric level, known as threshold scale inhibition, 100 80 Blank EDTA D. 2066 D. 2010 60 40 20 FIGURE 4: CaCO3 SCALE INHIBITION AT pH 10 38° FH 60° C 60 Time [min] Figure 2 demonstrates the relative peracetate stabilization effect under alkaline conditions for various sequestrants at two temperatures. The peracetate species formed by reaction of sodium perborate or sodium percarbonate and TAED in water are very sensitive to the presence of low Scale inhibition (%) 40 3.6 – Hydrolytic and Thermal stability DEQUEST® phosphonates have excellent hydrolytic stability compared with inorganic polyphosphates. This bond. Phosphonates can be used in hot or cold water at very high or very low pH for many hours without any trace not undergo hydrolysis in pH ranging from slightly acidic to strongly alkaline. DEQUEST® PB is not suitable for acidic formulation. NaOH D. 2016 D. 2066 D. PB 11620 D. PB 11625 AA/MA Copolymer 3.5 - Solubility DEQUEST® phosphonic acids and their salts are usually 0 20 2016DG are readily dissolved in water. crystal growth by adsorbing on crystal under formation.” 100 0 3.5.3 - Dry grades DEQUEST® PB grades exhibit good thermal stability and do 100 90 80 70 60 50 40 30 20 10 0 is due to the capability of the threshold agent to hinder phosphates, chlorides, etc. of decomposition. Kaolin dispersion - 1 % Kaolin Dispersed with 0.15 % dispersant "as is" at pH 10 Suspended material [%] 20 reduced in the presence of anions such as sulphates, property is linked to the extraordinary stability of the C-P After 22 weeks FIGURE 5: EFFECT OF DEQUEST® PRODUCTS ON KAOLIN 10 limit. The solubility of these salts can be significantly Dry DEQUEST® grades such as DEQUEST® 2016D and 50 70 0 Remaining Peroxide [%] stabilize particulate soil in the wash liquor and combined 60 50 80 Citric acid soluble in water and insoluble in organic solvents. Dry Gluconic acid DEQUEST® grades such as DEQUEST® 2016D and the 60 NTA DQ PB 11620 DEQUEST® 4000 series are quickly dissolved in water. 40 DQ PB 11625 They can also form oversaturated solutions which can be DQ 2060S DQ 2010 20 0 0.001 stable for years. For this reason, it can be difficult to establish thermodynamic solubility. 0.01 0.1 Log (Chelant/Ca++) molar ratio) 1 levels of transition or heavy metals. DEQUEST® 2066 is 10 DEQUEST® Products are excellent deflocculation agents of Figure 5 illustrates this effect by measuring the rate of 70 100 Shelf life (%) ON active acid – at pH 7 come very close to this solubility 3.4 – Deflocculation / Dispersion colloidal suspensions. In detergent applications, they bleaching process itself in the wash liquid as well as in the packaging, during the shelf life of the product itself. neutralization degree. The commercial 25% solutions – as PB series do not affect enzymatic ® clearly superior to the other sequestrants, it keeps its With DEQUEST® phosphonates, the scale inhibition sequestration power at both temperatures 40°C and 60°C. obtained at very low molar ratio (0.005 and less) is Aminocarboxylates such as EDTA and DTPA are more excellent. Between the threshold and stoechiometric area susceptible to N-oxydation than are aminophosphonates, lies an area of lower solubility of calcium phosphonates which is the probable reason of their poor performance. known as the turbidity region (see DEQUEST® 2010 curve). 3.5.1 - Acids The solubility of the acid form of HEDP (DEQUEST 2010) in water or acids is very high. The active ® acid of DEQUEST® 2060S is soluble at 50% concentration in very strong acids only, e.g. 15% HCl. More dilute solutions can be formed in aqueous systems. 11 Ingredients for Home Care Applications FIGURE 6: COTTON FIBRES AFTER 25 WASHES WITHOUT FIGURE 8: BLEACH STABILIZATION WITH DEQUEST® (a) AND WITH DEQUEST® (b). PHOSPHONATES - STANDARD P FREE DETERGENT 40°C, 20°GH - STABILIZER DEQUEST® 2066 AT 0.5 % AS ACTIVE DEQUEST® properties make them ingredients of choice for ACID Home Care products. Indeed, they prevent scale formation, disperse dirt, participate to the soil removal, and hinder Stain removal (%) bleach decomposition as well as metal corrosion. It translates in multiple benefits in the primary and secondary cleaning of Home Care formulations. 4.1 Laundry Because of their ability to inhibit scale formation arising from water hardness, DEQUEST ® products prevent incrustation of the linen and protect washing machine DEQUEST® colours or liquid detergents. This effect is less pronounced with DEQUEST® PB although stain removal improvement is also observed (Figure 10). 40 FIgURE 10: DEQUEST® IN HDL DETERGENT. REMOVAL OF 35 TEA AND WINE STAINS ON COTTON SWATCHES.” 30 60 25 50 20 Stain removal (%) 4 DEQUEST® in home care applications 15 10 a 5 tea 30 wine 20 10 0 heating elements. The combined dispersing and anti- 40 Blank scaling actions of DEQUEST prevent inorganic salts and ® 0 DEQUEST® 2066 WFK Tea BASE EMPA Wine DQ 2066 DQ 2016 PB 11625 PB 11620 PB 11615 particulate soil deposition that would otherwise result in greying of the linen (Figure 6). Of special interest is the FIGURE 9: DEQUEST® PB ADDDED TO THE WASH LIQUOR combined action of DEQUEST 2010 and DEQUEST PB ® (ppm ACTIVE) SOIL REMOVAL - BASE POWDER 6 G/L - 40°C that results in very low fibre incrustation (Figure 7). On the 50 ppm DEQUEST® 2010 IN THE WASH LIQUOR - other hand, the DEQUEST® PB series exhibit very good FIGURE 7: FIBRE INCRUSTATION PROTECTION WITH PRODUCTS (AA/MA: POLYACRYLIC/MALEIC b COPOLYMER) Phosphate-free Powder detergent - 7.75 g/l - 25 washes at 60 °C Ash residue [%] 4.1.1. Powder detergent 4 DEQUEST® products deliver enhanced cleaning and fibre 3,5 protection to powder laundry detergents. In bleach 3 containing detergents, the stabilization of oxygen bleach 2,5 2 by DEQUEST® phosphonates results in both enhanced 1,5 bleachable stain removal (Figure 8) and fibre protection. 1 Laundry powder detergents in general benefit from an 0,5 enhanced stain removal when formulated with DEQUEST® 0 Base Detergent + 2% + 4% + 0.1% AA/MA AA/MA HEDP + 2% PB 11620 + 4% PB + 2% PB 11620 11620 + 0.1% HEDP products. Indeed, DEQUEST® products contribute to the cleaning by loosening and dispersing the dirt through chelation of metals and adsorption on particulate soil (1) Laundry powder formulation LABS Ethoxylated fatty alcohol Zeolite 4A Na2CO3 Sodium silicate Na2SO4 Sodium Perborate Tetrahydrate TAED Fibre incrustation stabilizer : 10 :5 : 36 : 13 : 3.5 : 8.5 : 20 :4 : 0.1 – 4 % DEQUEST® PB 11615 DEQUEST® PB 11620 31 respectively. Particulate soil removal can be improved by the use of a an adequate combination of DEQUEST® phosphonate and DEQUEST® PB (Figure 8). Stain removal (%) DEQUEST 30 29 28 27 WASH LIQUOR – INCREASING AMOUNT OF DEQUEST® PB. 25 DEQUEST® PB 11615 DEQUEST® PB 11620 23 21 19 17 15 26 0 20 40 60 80 100 DEQUEST® PB addded to the wash liquor (ppm active) 25 0 50 100 150 200 DEQUEST® PB addded to the wash liquor (ppm active) Soil removal - Base powder 6 g/l - 40°C (3) ppm DEQUEST® 2010 in the wash liquor Heavy Duty50 Powder: - Increasing amount of DEQUEST® PB Sodium LABS Ethoxylated fatty Alcohol Zeolite 4A Na2CO3 Sodium Silicate Na2SO4 Sodium Perborate Tetrahydrate TAED 9.7 4.8 34.4 12.1 3.2 7.9 24.3 3.6 4.1.3. Laundry additives DEQUEST® products are ingredients of choice in laundry additives. On one hand, chlorine and oxygen bleach are effectively stabilized by DEQUEST® 2060 and DEQUEST® 6004. On the other hand, fabric conditioner benefits from the fragrances stabilization and preservative efficiency enhancement brought by the DEQUEST® phosphonate. 4.1.2 – Bleachable stains removal in absence of bleach (HDL) 4.2. Dishwashing The high stability constants of metal-phosphonate DEQUEST® products provide anti-filming, glass corrosion complexes are the basis for removing colour stains such inhibition, heating elements protection, stain removal and as wine, tea, coffee, etc… This well known property of bleach stabilization in automatic dishwashing detergents DEQUEST (ADD). ® 12 40°C40ºC – 30 MIN. 50 ppm DEQUEST® 2010 IN THE INCREASING AMOUNT OF DEQUEST® PB performance as anti-redeposition agent. ® FIGURE 11: TEA STAIN REMOVAL - BASE HDL 10 G/L - Stain removal (%) ® Phosphonates is particularly useful in peroxygen-free formulations such as powders for 13 Ingredients for Home Care Applications Stain removal enhancement resulting from the use of 5 Formulations 4.3. - Hard surface cleaning DEQUEST® phosphonates originates from their dispersing The combined dispersion and chelating properties of action on particulate soil, bleach stabilization and loosening of dirt by metal chelation (Figure 12 and 13). DEQUEST® phosphonates make them valuable grease 5.1 - Liquids cleaning booster. The DEQUEST When ® phosphonates and DEQUEST® phosphonates or DEQUEST® PB DEQUEST® PB ability to prevent spotting and filming is of carboxymethyl Inulin are used in liquid detergent FIGURE 12: VISUAL GRADING OF CLEANING EFFICIENCY special interest for glass and metal cleaning. For the latter, formulations, they are most easily formulated by mixing a OF NORMAL WASH PROGRAM (55°C, 8-10° DH, FRESENIUS DEQUEST FEBRUARY 2006) and magnesium salts which would otherwise be 6,9 8,0 7,0 6,9 8,6 (See Figure 14 for DEQUEST® PB). 8,4 9,0 8,7 8,5 8,8 9,0 9,0 responsible for filming and spotting on glass and china. 10,0 6,0 Standard ADD product : 5,0 1. With 40 % STPP 4,0 2. With 40 % Citrate 2,7 Cleaning Score (10 = max.) useful to prevent the formation of large crystals of calcium 3,0 2000 and DEQUEST 2010 provides mild liquid grade DEQUEST® or DEQUEST® PB into the detergent. stainless corrosion inhibition. Bleach containing cleaners The pH can be adjusted with caustic or triethanolamine benefit from the presence of DEQUEST® 2060 or after DEQUEST® 6004 for oxygen and chlorine bleach concentrated DEQUEST® grades, DEQUEST® 2060S (50% stabilization respectively. Bleach free cleaners take active) and DEQUEST® 2010 (60% active), which provide a advantage of DEQUEST® phosphonates that bring better flexibility in liquid applications than do the additional cleaning power especially on coloured stains conventional phosphonate salt solutions. ® ® mixing. Italmatch Chemicals S.p.A. supply such as tea, coffee, wine… 2,0 3. With 40% DEQUEST® PB 11620 5.2 - Powders, granules and tablets 1,0 4. With 50% DEQUEST PB 11620 DEQUEST® 5. With 25% Citrate + 25% DEQUEST® PB 11620 carboxymethyl Inulin can be applied in granulated or 0,0 ® Oat Flakes Minced Minced Meat 120°C Meat 200°C P-free with DEQUEST® PB Milk Tea phosphonates and DEQUEST® PB powder detergents by direct mixing of a solution in the Reference (IEC - B) During the dishwashing process, the glass tends to be crutcher or by spray-drying the neutral or alkaline solution progressively “dissolved” in water based media. This on a granular detergent base. Some precautions should be FIGURE 13: GRAVIMETRIC EVALUATION OF CLEANING phenomenon is much more pronounced in soft water and taken in these processes. When phosphonates or EFFICIENCY OF NORMAL WASH PROGRAM (55°C, 8-10° is catalyzed by pH above 9. This results in scuffed glass. carboxymethyl Inulin are sprayed on a granulate detergent base, the perborate or percarbonate should be added DH, FRESENIUS FEBRUARY) 2006 Lab experiments demonstrate that DEQUEST PB has a after the spraying of DEQUEST® or DEQUEST® PB. The protective effect against glass corrosion occurring in the thermal stability of DEQUEST® and DEQUEST® PB are high course of the dishwashing process (Figure 15) enough to allow spray-drying in any type of equipment 98 99 82 90 80 without adverse effects. 70 60 50 40 FIGURE 15: GLASS WEIGHT LOSS AFTER 7 HOURS DEQUEST® phosphonates can also be incorporated by IMMERSION IN WATER post-addition of powders or granules. In this case, no special precautions other than the standard product safety 30 Egg/Milk Egg Yolk 10 0 0.008 Starch - mix PF-free with DEQUEST® BP Reference (IEC-B) Carbonates and silicates present in automatic dishwashing product (ADD) stimulate the precipitation of water hardness forming insoluble silicates and carbonates with calcium and magnesium. Although handling procedures have to be taken. Italmatch Chemicals 0.007 Weight loss (%) 11 20 8 % Cleaning (100% = max.) 100 99 ® 0.006 11°FH S.p.A. can supply DEQUEST® phosphonate powders or 0.005 22°FH granules with a granulometry typical for detergent 0.004 33°FH powders. 0.003 The following solid grades of DEQUEST® phosphonates 0.002 are available for detergent applications: 0.001 0 Brand Leader from Market Base + DQ PB12625 Sodium Tripolyphosphate (STPP) is still the most widely used Glass immersion during 7 hours with products dosed builder in these formulations, there is more and more R&D @ 4.5 g/l in water @ 60°C Chelants are added as effort devoted to the development of “P-Free” or “Low-P” 6.5 %w of the Base DEQUEST® 2016D: powder form of DEQUEST® 2016 DEQUEST® 2016DG: granular form of DEQUEST® 2016 builder systems. DEQUEST® phosphonates and DEQUEST® PB, owing to 14 their threshold scale inhibition properties, are particularly 15 Ingredients for Home Care Applications Phosphonates are not readily biodegradable in laboratory semi-continuous activated sludge tests, but in more realistic die away rivers tests they are rapidly degraded in sunlight FIG 16: DAPHNIA IMMOBILISATION TEST (OECD 202). proved to be completely mineralised in sewage water Table 9 provides an overview of the aquatic toxicity of EFFECT CONCENTRATION (EC) AFTER 48 H. treatment systems (1). 8000 tests were conducted in accordance with OECD standard 7000 during 6000 intermediaries released up to a concentration of 1 g/l had 5000 no toxic effects on Daphnia. Given the similarity of the 4000 structures, it can be reasonably anticipated that DEQUEST® 3000 PB degradation products exhibit a similar low toxicity guidelines. TABLE 9: ECO-TOXICITY OF DEQUEST® PB 11620 FOR AQUATIC ORGANISMS in the presence of ferric ions. Organism Bacteria EC10 > 10000 DIN 38412 Daphnia EC0 (t 48h) 2000 OECD 202 EC50 (t 24h) 5500 OECD 202 EC50 (t 48h) 2900 OECD 202 LC0 (t 96h) > 10000 OECD 203 rapidly eliminated by fish. treatment with aluminium sulphate or lime; treatment of drinking water by chlorine or ozone also destroys phosphonates. Test mg.l-1 They do not bio-accumulate in aquatic species and are They can be eliminated from waters by classical water Toxicity Effect They are also degraded in soil, species of Pseudomonas have been shown to be able to feed on phosphonates. Fish low and phosphonates partition rapidly to sediments from water. No toxicity was found for either bacteria (Pseudomonas Putida) or for the zebra fish, using the maximum applied Given that daphnia is the most sensitive organism, the influence of the derivation level (DS) on the toxicity for this organism was studied. The results are shown in fig. 9. It can be concluded that the toxicity (indicated by the 6.2. Environmental profile of DEQUEST® PB immobilisation) increases with an increase in the The good environmental profile of DEQUEST PB makes derivation level. However, the aquatic toxicity of the highly carboxymethyl Inulin an excellent formulation ingredient substituted DEQUEST® PB 11620 is extremely low (factor for detergents designed to meet the requirements of the 10-20) compared to that of polyacrylates. ® European Eco-label or other special industry or national environmental standards. 2000 the degrading of carboxymethyl cellulose, profile. 1000 0 concentration of 10 g/l. Mobilization of heavy metals from sediments is extremely A study conducted by Sieger and others (2) showed that DEQUEST PB products for bacteria, daphnia and fish. The ® Concentration (mg/l) 6.1 - Environmental profile of DEQUEST® phosphonates 6.2.1. Eco-toxicity of DEQUEST® PB EC 0 EC 50 AKZO NOBEL – Environmental fate of CMC Sieger, C.H.N., Kroon, A.G.M., Batelaan, J.G. & van Ginkel, C.G. in Biodegradation of carboxymethyl cellulose by Agrobacterium CM-1. Carbohydrate Polymers, 27, 137-143, (1995) EC 100 PB 11620 PB 11615 PB 11610 6.2.2.Biodegradability of DEQUEST® PB Substances that qualify as inherently biodegradable are assumed to be degradable in the natural environment. The Semi-Continuous Activated Sludge (SCAS) test (OECD 302A) is used to determine inherent biodegradability. All DEQUEST® PB products satisfy the criteria (daily degrading >20%) for inherently biodegradable substances. FIG.17 DAILY DEGRADATION IN OECD 302 SCAS TEST 30 25 % Biodegradation 6 Environmental Data 20 15 10 5 0 PB 11610 PB 11615 PB 11620 The inherent biodegradability gives the product a certain amount of microbiological stability. This is especially important in systems in which the product stays in the system over a period of time because it is recirculated. Far fewer preservatives are used then with readily biodegradable products, and lower doses are sufficient. The results in the simulation test correspond with the findings for carboxymethyl cellulose (CMC), which has 16 17 Ingredients for Home Care Applications 7 Handling 6.2.3 - Other environmental aspects In a Life Cycle Analysis (LCA), products with comparable functions are evaluated “from cradle to grave” for a broad range of possible environmental effects (including the greenhouse effect, acidification, etc.). In addition to extremely low (eco) toxicity and the (inherent) biodegradability, the agricultural origin of the raw material (biopolymer) has more advantages for the environment than petrochemical-based products such as fewer CO2 emissions and less contribution to the depletion of fossil fuels. Furthermore, the DEQUEST® PB products contain no nitrogen or phosphorous, which means that when released in the environment, they do not contribute to acidification, fertilisation (enrichment of soil and water with mineral nutrients that increase productivity) or eutrophication. DEQUEST® phosphonates 8 Quality of DEQUEST® products and DEQUEST® PB carboxymethyl Inulin appear to possess no acute DEQUEST® products are covered by certification to quality standard ISO 9002. toxicological properties which could require special handling other than good hygienic practices used with any In addition, the Newport (UK) Dequest manufac-turing site industrial chemical. Special attention should be paid to is certified to the Environment Management System avoid eye and skin contacts. Standard ISO 14001. It also participates in the European Community EMAS regulation (Eco Management Audit DEQUEST® 2060S contains free HCl in solution and should Scheme) which requires independent verification of be handled accordingly, in well ventilated areas. environmental performance. In case of skin contact with DEQUEST® phosphonates or DEQUEST® PB, wash thoroughly with soap and water. In case of eye contact, flush immediately with large volumes of water for at least 15 minutes. If irritation persists, consult a physician. Over and above the points already mentioned, particular care should be taken when handling members of the DEQUEST® 2040 series: wear gloves, eye protection and avoid breathing dust from solid products. Provide local exhaust ventilation. If dust is a problem, wear suitable respiratory protection. Wash thoroughly after handling. More detailed information on safety and environmental aspects of phosphonates can be provided by Italmatch Chemicals S.p.A. upon request. Before using DEQUEST® phosphonates or DEQUEST® PB carboxymethyl Inulin, please also consult the relevant Material Safety Data Sheets and carefully observe the statements concerning toxicity, safe handling and first aid procedures. 18 19 Ingredients for Home Care Applications More information If you would like to obtain more detailed information about DEQUEST® products or are interested in obtaining a sample for evaluation in your system, please contact your nearest Italmatch Chemicals S.p.A. representative or visit our website: http://www.dequest.com Italmatch USA JAPAN OFFICE North American Headquarters ITALMATCH JAPAN LTD 21 East Front Street Burex Kojimachi 5F, Red Bank, NJ 07701 3-5-2 Kojimachi, Chiyoda-ku USA Tokyo 102-0083 Tel: (732) 383-8500 Japan Fax: (732) 383-8407 Tel: +81 3 5210 3811 info@Italmatchgroup.com Fax: +81 3 5210 3830 info@italmatchgroup.com CHINA OFFICE ITALMATCH INTERNATIONAL TRADING SINGAPORE OFFICE (SHANGHAI) CO., LTD ITALMATCH SINGAPORE PTE LTD Room 703, Pine City, No. 1 Kim Seng Promenade 8 Dong`an Road, Xuhui District, #17-02 Great World City East Tower Shanghai 200032 Singapore 237994 P.R. China Tel: +65 6235 6483 Tel: +86 21 3469 1871 Fax: +65 6836 4534 Fax: +86 21 3469 1872 infoasia@italmatchgroup.com Belgium (Marketing and Innovation Center) Italy (Europe/Africa/Middle East Customer ITALMATCH BELGIUM SPRL Service Center) Parc Scientifique Fleming Italmatch Chemicals S.p.A. Rue Laid Burniat 3 Via Vismara 114 1348 Louvain-La-Neuve 20020 Arese Belgium Italy Tel: +32 (0) 10 48 12 11 Tel: +39 02 93525237 Fax: +32 (0) 10 48 14 95 Fax: +39 02 93525496 info@Italmatchgroup.com customercare@italmatchgroup.com The information in this bulletin is to the best of our knowledge true and accurate but all instructions, recommendations or suggestions are made without guarantee. Since the conditions of use are beyond their control, Italmatch Chemicals S.p.A. and its subsidiaries disclaim any liability for loss or damage suffered from use of these data and suggestions. Furthermore, no liability is accepted if use of any product in accordance with these data or suggestions infringes any patent.