Pigments & Additives Division Specialties Business

Exactly your chemistry.

Hordaphos

High performance for cleaning products

High performance for cleaning products

Phosphoric acid

HO P HO

O OH

Phosphoric acid monoester

HO P HO

O OR

Phosphoric acid diester The product group encompasses a wide range of different phosphoric acid esters. As multifunctional additives they are used especially in household and professional cleaning products, but also in pigment pastes, paints, cosmetics, in formulations for metal working and metal cleaning, in textile production, crop protection, mining etc. Depending on the Hordaphos grade, the substance acts as a mild acid, corrosion inhibitor, Hordaphos brightener, antistatic agent, wetting agent, dispersing and/or emulsifying agent. Hordaphos grades substantially improve the performance of cleaning products. The Hordaphos grades are produced by the reaction of phosphorus pentoxide or polyphosphoric acid with an alcohol, whereby a mixture of mono-, di- and triester is obtained.

HO P RO

O OR

Phosphoric acid triester

RO P RO

O OR

acidic
lime and rust dissolving

HO

O P phosphatizing
corrosion inhibiting

anionic
antistatic

O H+

O-R multifunctional
foam regulating hydrophobic corrosion inhibiting emulsifying dispersing solubilizing wetting

That means that phosphoric acid esters can be regarded as a combination of phosphoric acid plus one to three alcohol group(s) R. A phosphoric acid ester is acidic as phosphoric acid and has similar phosphatizing properties. Due to the additional alcohol chain it is far less corrosive. The ionic phosphate functionality imparts antistatic properties to the molecule. Furthermore, when combined with a long chained alcohol the substance (e.g. Hordaphos 222) can be given strong dispersing properties. Thus, depending on the chain length and branching of the alcohol, the Hordaphos grade can be emulsifying, foam-regulating, dispersing, wetting, dissolving etc. Short-chain phosphoric acid esters are sold under the trademark Hordaphos CC grades. In aqueous solution they act as proton donors and are much less corrosive than free mineral acids. They are therefore a good choice as suitable base substances for acidic cleaning. In particular, they can be relied on to remove mineral-based deposits such as lime. In this regard the combination of strong cleaning power and high anticorrosive effect is a distinguishing mark of the Hordaphos CC grades.

With increasing chain length the hydrophobic content of the molecule gradually predominates, solubility in water declines and acidity is reduced. Hordaphos MDGB is a strong corrosion inhibitor for acidic media while still being very freely soluble in water. For alkaline formulations the neutralized Hordaphos 136 with a longer chain length is recommended. Phosphoric acid esters with even longer chain lengths are Hordaphos MDO, Hordaphos 222 and Hordaphos MDST. These products are emulsifiable in water. Depending on their chemical structure these phosphoric acid esters show interesting dispersing and wetting effects. They can also act as antistatic agents, defoamers or foam stabilizers. The Hordaphos grades properties are summarized in the table on pages 10 and 11.

Cleaning enhancer with built-in corrosion protection

Removing limescale or rust is a major challenge in many fields of application. Examples are limescale in bathrooms, kitchens and swimming pools or rust and greasy dirt and grime from trams, buses, trains, cars and wheels. Strong acids remove such deposits easily but they also attack and damage the surface. Iron and steel in particular as well as aluminum alloys are attacked severely by inorganic and organic acids, but plastic, glass and ceramic surfaces are also corroded by strong chemicals. The corrosivity of these acids in aqueous solution can be substantially reduced or even completely eliminated by suitable inhibitors such as phosphoric acid esters, e.g. Hordaphos MDGB (Fig. 2). Another elegant way to combine strong cleaning power with high surface protection is to use the Hordaphos CC grades or Hordaphos MDE. These are effective acidic cleaning agents with very low corrosion potential.

Hordaphos CC grades mild but efficient acid > effective in cleaners for household, sanitation, automotive and food processing industries > excellent cleaning performance and high limescale-dissolving power > low corrosion rates on metallic (Fig.1) and non-metallic materials > higher solubility for various salts and oxides than phosphoric acid: prevention of precipitates > remove mineral-based deposits (lime, cement and efflorescence) > remove oxidation or corrosion deposits (ferric oxides, manganese oxides, etc.) > effective even in hard water > are recommended as base components for acidic cleaners

Corrosivity and lime dissolution efficiency of acids compared to Hordaphos CC grades.

Weight loss caused by corrosion [g/d.m 2] 300 Lime dissolution effiency [%] 250 200 150 100 50 0 100 80 60 40 20 0

Phosphoric acid H3PO4

Sulfamic acid NH2(SO3H)

Formic acid HCOOH

Hydrochloric acid HCl

Sulfuric acid H2SO4

Hordaphos CC MS

Hordaphos CC MIS

Weight loss of steel caused by corrosion (weight loss in gram per day and square meter; DIN 50905) Limescale dissolution efficiency %

Figure 1: Corrosivity and lime dissolution efficiency of different acids (10 % solution) compared to Hordaphos CC grades Hordaphos CC grades possess very low corrosion potential combined with high limescale-dissolving power.

Hordaphos MDGB strong corrosion inhibitor for various acids > effective corrosion inhibitor for acidic aqueous systems > substantially reduces the corrosivity of various acids: sulfamic acid, phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, maleic acid, malic acid, glycolic acid, etc. (Fig. 2) > works on common metal surfaces (e.g. steel, copper, different alloys) > effective in cleaners for the food processing industry

Corrosivity of different acids with and without Hordaphos MDGB

Weight loss caused by corrosion [g/d.m 2] 250 200 150 100 50 0 Sulfamic acid NH2(SO3H) Phosphoric acid H3PO4 Hydrochloric acid HCl Sulfuric acid H2SO4

Corrosion on steel without MDGB Corrosion on steel with 1 % MDGB Figure 2: Weight loss of steel caused by corrosion: Corrosivity of different acids (10 % solution) with and without the addition of Hordaphos MDGB (weight loss in gram per day and square meter; DIN 50905). The presence of Hordaphos MDGB substantially reduces the corrosion rates.

Hordaphos 136 corrosion inhibitor for neutral and alkaline media > liquid neutralized phosphoric acid ester > effective corrosion inhibitor for neutral or alkaline aqueous systems > detergent booster due to its good wetting and dispersing ability

Hordaphos MDE cleaning agent for metal surfaces > effective in acidic pickling and degreasing agents for derusting and degreasing for industrial metal cleaning > effective cleaning additive for the building and sanitation sectors > produces high-gloss effect on chromium, stainless steel, copper, brass, etc. > antistatic agent > soluble in water and oil > wetting agent

Power for industrial and institutional cleaning

Powerful cleaning agents are needed in industries such as abattoirs, meat processing plants and dairies as well as engineering workshops or garages. Hordaphos 136 and Hordaphos MDO have been especially developed to act as powerful wetting and dirt suspending agents to remove oil and grease (Fig. 3). These Hordaphos grades are particularly effective in removing partially dried blood, fat, casein residues, rust, paint and stubborn stains from various surfaces.

Neutral cleaner with 5 % Hordaphos MDO Good wetting and emulsifying action

Neutral cleaner without Hordaphos

Neutral cleaner with 5 % Hordaphos 136 Excellent wetting action

Figure 3: Removal of grease with Hordaphos MDO or Hordaphos 136, demonstrated with colored mineral lubricating grease.

Hordaphos 136 booster for neutral cleaners > excellent wetting effect > shows strong dispersing properties > effective corrosion inhibitor in aqueous systems at pH > 6 > neutralized phosphoric acid ester Hordaphos MDO cleaning enhancer and foam stabilizer > foam stabilizer (see guide formulation on page 8) > strong emulsifying and dispersing properties > high cleaning efficiency (low concentration necessary) > acidic phosphoric acid ester with high alkali stability

The added extra for liquid and solid detergents

Washing powders and liquid detergents are multifunctional blends. Hordaphos 222 as additive substantially improves the wearer comfort and handle of garments after washing. Furthermore it shows excellent dispersing action in detergents. Hordaphos MDST is particularly effective in reducing foam at elevated temperatures. Excessive foam can have adverse effects on machine performance resulting in reduced efficency in detergency and cleaning.

Soapy water

Soapy water 0.2 % Hordaphos MDST

Figure 4: Defoamer Test (Perforated disc beating method; DIN EN 12728) with and without Hordaphos MDST at room temperature (Hordaphos MDST was dissolved at 60 C).

Hordaphos 222 for liquid detergents and dry cleaning > good antistatic and softening effect on laundry > suitable especially for liquid wool detergents, mild detergents and fabric softeners > excellent emulsifying action for water in chlorinated hydrocarbons and petroleum spirit > recommended for dry cleaning agents Hordaphos MDST efficient defoamer for high-temperature detergents > foam regulating effect is activated at temperatures between 60C and 90C > highly effective only low concentration neccessary > works in soft and hard water > solid phosphoric acid ester > especially recommended for solid detergents

Guide Formulations

These basic guide formulations can help chemists use their expertise to develop their own end products.

Lime cleaner This lime cleaner shows high efficiency against lime deposits, e.g. from coffee machines, bathroom fittings or stainless steel sinks. The use of Hordaphos MDGB as a corrosion inhibitor improves the cleaning effect on aluminum, stainless steel or acid-proof enamel surfaces. The formulation components are mixed at room temperature in the given amount of water. The formulation can be used both for cold and warm applications. The recommended application is a 10 % dilution in water.

Foam cleaner This special, high-foaming alkaline cleaner forms a voluminous, highly adherent foam when a foam lance is used in combination with high-pressure equipment. This foam effortlessly removes dirt in the form of partially dried blood residues, fats and casein residues on tiled walls and floors or stainless steel surfaces e.g. in abattoirs, sausage factories, butchers shops, dairies and other food processing factories.
Hordaphos MDO stabilizes the foam and improves the wetting power of the foam cleaner. The formulation constituents are mixed at room temperature in reverse order. When used on sensitive surfaces, e.g. glossy surfaces, aluminium or aluminium alloys, a preliminary test for material compatibility should be carried out.

Neutral cleaner (see page 6, Fig. 3) All-purpose cleaners should be capable of removing a wide variety of dirt and soil even at a neutral pH. This formulation is noted for the fact that, even in the technical sector, dirt such as cutting fluids and greases as well as mineral deposits can be removed completely. Hordaphos 136 not only acts as an effective corrosion inhibitor but also ensures excellent cleaning results due to its dispersing and emulsifying properties.
The components are mixed at room temperature in reverse order. The cleaner is used in a dilution of about 1:10 to 1:100 with water, depending on the degree of soiling. In the case of severe soiling, concentrated solution can be used.

1.5 % Hordaphos MDGB 1) 10.5 % Sulfamic acid 88.0 % Water 0.01 % Vitasyn Blue AE 90 1)

3.0 % Hordaphos MDO 1) 7.0 % Sodium cumenesulfonate, 40 % solution 5.0 % Genapol UD 079 2) 14.0 % Tetrapotassium pyrophosphate, 60 % 9.0 % Potassium hydroxide solution, 50 % 5.0 % Potassium silicate, 28-30 B 57.0 % Water

5.0 % Hordaphos 136 1) 3.0 % Genapol UD-079 2) 2.0 % Hostapur SAS 60 2) 3.0 % Isopropanol 2.0 % Butyl diglycol 2) 0.5 % Trilon A 3) 84.5 % Water 0.01 % Sanolin Green G-39L 1)

1) = Clariant, Division Pigments & Additives 2) = Clariant, Division Functional Chemicals 3) = BASF

Tile cleaner If tiled walls are cleaned with mineral acid-based products and/or organic acids often the joint filler corrodes. As a result it becomes sandy or efflorescences occur. This is initially an unpleasant visual problem but may result, in extreme cases, the tiles becoming loose. Hordaphos CC additives improve the effectiveness and considerably lower the aggressiveness of the cleaner. The citric acid is dissolved in the given amount of water, the detergents are added while stirring, after which the corresponding amounts of phosphoric acid and Hordaphos CC MS are incorporated. Depending on the degree of soiling the approx. 1:10 to 1:100 diluted concentrate is applied to the prewetted soiled surface and rinsed off with cold or hot water after approx. 15 minutes.

Glass cleaner When glass panes and car windows are cleaned, soot, dust, pollen and fat have to be removed completely, leaving a smear-free result. On the other hand, adjacent materials such as rubberseals, plastic or paint must not be damaged. Formulations based on isopropanol and Hordaphos CC MIS are recommended for a satisfactory cleaning result. Hordaphos substantially lowers the corrosive potential of the formulation. First the surfactants are dissolved in the given amount of water, then Hordaphos CC MIS and isopropanol are added while stirring. Application concentration: 1:50 to 1:100.

Rim cleaner Cleaners based on sulfuric or hydrochloric acid are suitable for performing a heavy duty job on highly contaminated surfaces, e.g. rims. Unfortunately these acids strongly attack the surface to be cleaned as well as the dirt and may form precipitates in hard water. With Hordaphos CC additives, however, these undesired side effects of cleaning operations are virtually nonexistent. The formulation easily removes oil, grease and dirt as well as rust and thus restores the rims to their original shiny state without corroding other parts of the coachwork. The detergents are mixed in the order given and then the specified amounts of Hordaphos CC MIS, butyl glycol and lastly water are added. Application concentration: 1:10 to 1:20.

5.0 % Hordaphos CC MS 1) 5.0 % Phosphoric acid 85 % 5.0 % Citric acid monohydrate 3.0 % Genamin O 080 2) 3.0 % Genapol UD 080 2) 79.0 % Water

2.0 % Hordaphos CC MIS 1) 0.3 % Genamin O-080 2) 0.3 % Genapol OX-100 2) 10.0 % Isopropanol 87.4 % Water 0.01 % Sanolin Blue NBL

20.0 % Hordaphos CC MIS 1) 5.0 % Hostapur SAS 60 2) 3.0 % Genapol UD 050 2) 5.0 % Genapol X 080 2) 3.0 % Butyl glycol 2) 64.0 % Water

Hordaphos product overview

Hordaphos CC MN
Chain length Phosphorus content [%] Viscosity at 20/25 C [mPas] 1 26.0 50 930 1.7 soluble colorless liquid 54 1.55

Hordaphos CC MS
1 27.0 200 980 1.3 soluble colorless liquid 63 1.55

Hordaphos CC MIN
1-3 24.0 70 850 1.8 soluble colorless liquid 61 1.48

Hordaphos CC MIS
1-3 24.0 1000 810 1.2 soluble colorless liquid 59 1.39

Technical Data Application properties Main application

Acid number [mg KOH/g] pH at 20/25 C, 10 g/l H2O Solubility in water at RT Color State at RT Surface tension (Noy at 25 C 5 g/l) [mN/m] Density at 20 C [g/cm 3]

Corrosion inhibition Mild acid with low corrosion potential Dissolving limescale Rust removal Enhancing cleaning Wetting effect Dispersing effect Polishing effect on metals Antistatic effect Foam stabilization Defoamer Rinse aid

Acidic cleaners Alkaline cleaners Neutral cleaners

* = in neutral and alkaline medium **EO = Ethylene oxide units

10

Hordaphos MDE
2 22.6 280 690 1.5 soluble colorless liquid 61 1.32

Hordaphos MDGB
2-4 19.5 1100 650 1.7 soluble colorless liquid 43 1.35

Hordaphos 136
8 6.7 29800 6.7 soluble yellow to brownish liquid 27 1.11

Hordaphos MDO
8 11.5 250 330 2.7 emulsifiable colorless liquid 24 1.02

Hordaphos 222
12 + 4 EO** 4.8 500 140 2.4 emulsifiable colorless liquid 28 1.02

Hordaphos MDST
18 6.4 180 2.3 emulsifiable white solid 40 1.03

11

Please note This information is based on our present state of knowledge and is intended to provide general notes on our products and their uses. It should not therefore be construed as guaranteeing specific properties of the products described or their suitability for a particular application. Any existing industrial property rights must be observed. The quality of our products is guaranteed under our General Conditions of Sale.
= Trademark of Clariant registered in numerous countries Edition: March 2004

Exactly your chemistry.

www.pa.clariant.com Clariant International Ltd. Pigments & Additives Division Marketing Specialties Business Rothausstrasse 61 4132 Muttenz Switzerland Phone: +41-61-469-7975 Fax: +41-61-469-7577

Clariant Produkte (Deutschland) GmbH Division Pigments & Additives Business Unit Specialties 65926 Frankfurt am Main Germany Phone: +49-69-305-21311 Fax: +49-69-305-89539

DA 7200 E_03/04