Product Information EURECO TM. ε-phtalimido-peroxy-hexanoic acid (PAP) CleanCare

Transcription

1 Product Information EURECO TM ε-phtalimido-peroxy-hexanoic acid (PAP) CleanCare

2 Index of contents INTRODUCTION 4 EURECO TM 4 EURECO commercial grades 5 Solid grades 5 Liquid grades 6 Application Bleaching Efficiency 7 Influence of washing bath ph value 8 Colours and fibres damage evaluation 10 Low wearing of textiles 11 PAP compatibility with enzymes 12 Disinfection 14 Trends of Washing 14 EURECO registration in the BPD positive list 16 Usage of EURECO in detergent 17 Grades for I&I 17 EURECO LX10/LX17/LX20 17 Grades for consumers 19 EURECO LX5 19 EURECO LX5V 21 Regulations 21 Appendix 22

3 Index of figures Application Bleaching Efficiency 3-1: Bleaching performance of PAP vs. persalt and persalt + TAED in function of temperature 7 3-2: Comparison of bleaching performance in heavy duty detergency 8 3-3: The influence of ph on the bleaching performance of PAP 9 3-4: Dye fading on coloured cotton after 40 wash cycles at 25 C : Cotton fabric resistance after 30 wash cycles at 25 C : Cotton fabric resistance after 25 wash cycles at 60 C : Textile damage PAP vs. chlorine bleach : PAP compatibility with enzymes : Bleaching effect of PAP in light duty detergent 13 Disinfection 4-1: Trend of washing temperature : Residual bacterial load after washing at different temperatures : Sanitizing effect of PAP in washing liquor at 40 C 15 Usage of EURECO in detergent 5-1: Performance: High bleach efficiency effect of 340 mg/l of PAP : Light duty washing: overall performance at T = 20 C, t = 30 min : Heavy duty washing: overall performance at T = 40 C, t = 30 min 20

4 EURECO 4 INTRODUCTION ε-phthalimido-peroxy-hexanoic acid (PAP), produced over the past ten years, has gained extensive experience in the handling, storage and use of this innovative chemical. In the early days of its industrial production, the principal use of PAP was to serve as a bleaching agent; however, in the recent years many other applications have been found for example in the field of chemical synthesis, personal care, agriculture, surface cleaning and most of all disinfection. One of the major advantages of PAP over most other oxidising agents used in industry is its outstanding physical stability coupled with its crystallinity. This feature renders PAP easy to handle and storable according to the requirements for the least hazardous class of Organic Peroxides, thus allowing for its use in household consumer products. PAP preparations are commercialised under the trade name of EURECO TM. PAP is produced by: EURECO is a registered trademark of the company: EURECO EURECO is the registered trademark of Solvay for its commercial preparations based on PAP, a preformed peracid patent. ε-phthalimido-peroxy-hexanoic acid (PAP) PAP is part of the chemical family of peroxycarboxilic acids which is produced in Italy under proprietary technology.

5 TM Introduction 5 EURECO is an auxiliary material for detergents and biocidal compositions, which readily delivers superior bleaching and disinfecting performance at a low temperature and under mild conditions. PAP is a white substance, sparingly water-soluble, crystalline, high-melting, odourless, very active but non-aggressive to human beings. Thanks to its 5.7 % of readily-available, high-potential AvOx (active oxygen: molecular weight of PAP = 277 g/mol), PAP easily outperforms persalts and hydrogen peroxide with a weight factor 10. The eco/toxicological profile is exceptionally favourable No long-term/chronic effects Non-toxic to human beings Inherently biodegradable PAP is registered in the official lists of the Chemical Products admitted without limitations to the markets of the main countries: European Union (ELINECS/level 2), USA, China, Japan, South Korea, Australia and Canada. EURECO commercial grades Solid grades EURECO WM1 powder (71 % active PAP), bleaching and disinfecting agent. Applications (as is): Bleach booster for I&I Disinfecting aid for I&I Hygienic additive for I&I

6 EURECO 6 Liquid grades EURECO LX10, LX17, LX20 white milky aqueous composition based on PAP crystals, suitable for delivering high PAP level in total safety and without restrictions. It is suitable as liquid intermediate for consumer products or as I&I bleaching and disinfecting chemical. Applications (as is): Liquid bleach booster for I&I Disinfecting aid for I&I Hygiene aid for I&I Hard surface cleaning for consumer and I&I Anti-mould cleaner Disinfection of cattle Disinfection of meat processing lines EURECO LX5 white milky aqueous composition based on very tiny PAP crystals, suitable as ready to-use-additive or in combination with liquid or solid detergents and in pre-packed delivery systems. It exploits superior bleaching performance and biocidal activity against a wide spectrum of germs and bacteria. Applications (as is): Bleach system in dual compartment heavy/light duty liquid detergents Bleach system in dual compartment compact heavy/light duty liquid detergents Liquid bleach booster (optionally with fragrance and surfactants) Hygiene aid Hard surface cleaning Anti-mould cleaner Disinfection of cattle EURECO LX5V white milky aqueous composition based on very tiny PAP crystals and additional surfactants, is expressly designed for those applications where high viscosity and wetting or mild detergency capacity are required. Applications (as it is): Pre-spotter Liquid bleach booster Hard surface cleaning

7 TM Bleaching Efficiency 7 Application Bleaching Efficiency In order to have a general picture regarding the bleaching performance of PAP in comparison with those of persalt alone and of persalt activated by TAED, in figure 3-1, the results of different stains removal are reported in function of the washing temperature for the three bleaching systems obtained in normal washing conditions Performance (%) PAP Persalt + TAED Persalt 10 Best T range 0 for PAP T ( C) Figure 3-1: Bleaching performance of PAP vs. persalt and persalt + TAED in function of temperature It can be derived that: already at 30 C PAP can produce the bleaching efficiency obtainable by the other two bleachers at much higher temperatures only the highest difference in performance between PAP and the activated persalt is in the range C above 40 C, the higher the temperature, the lower the difference between PAP and the activated persalt The diagram confirms that the ε-phthalimido-peroxy-hexanoic acid is particularly active at low temperatures and that the best advantages come from the use of PAP in the range C.

8 EURECO 8 Reflectancy Values (%) PAP dosage = 1/4 w/w of PCS + TAED HD Detergent + PAP HD Detergent + PC + TAED T = 30 C T = 60 C T = 30 C T = 30 C T = 60 C T = 30 C wfk Grass EMPA 164 wfk Redwine 10L Figure 3-2: Comparison of bleaching performance in heavy duty detergent As an example, in figure 3-2, the comparison between the bleaching power of a HD detergent containing PAP and another containing PC and TAED at two different washing temperatures (30 and 60 C), tested on two different standard stains (grass and red-wine) is recorded. As can be seen, at 30 C PAP performs much better than the normal detergent at the same temperature and produces comparable results with those obtained by the PC/TAED bleach at 60 C. It is also important to underline that this occurs using amounts of PAP much lower than the mixture PC/TAED; in practice, the recommendable dosage of PAP is roughly 1/4-1/5 by weight of the persalt + TAED mixture. In the case of traditional heavy duty detergents this means a dosage of PAP ranging from 5 to 6 %. Influence of washing bath ph value To achieve this outstanding performance of PAP, it is recommendable to operate with a buffered system to ensure a good control of the washing bath ph. In fact, the highest bleaching performance of ε-phthalimido-peroxy-hexanoic acid, that means the best activity of the active oxygen of the peroxide group, is strictly connected with ph values close to 8.5. This is due to the fact that this ph value is very similar to the pka value of the peroxy acid group in the PAP molecule. According to the equilibrium reaction below, under these conditions the acid form and the anionic form of PAP have practically the same molar concentrations and they build up a particular 1 : 1 complex which displays the highest efficiency. C13H14NC=O-O-OH (PAP) C13H14NC=O-O-O - + H +

9 TM Bleaching Efficiency 9 Reflectancy Values (%) PS + TAED (HD ph 10.5) PAP (HD ph 10.5) PAP (HD ph 8.7) PAP (HD ph 9.5) Grass EMPA art C 30 C 40 C Figure 3-3: The influence of ph on the bleaching performance of PAP The bleaching performance has been tested on different standard stains (wine-tea-grass EMPA stains) at three different temperatures (T = 20 /30 /40 C) and three different ph conditions. The tests show that: the bleaching power of PAP is more strongly affected by ph than expected at ph 10.5, that is the usual ph of traditional heavy duty detergents, the PAP performance is far from the achievable value at lower ph working at ph 8.7 the best results are obtainable, thus confirming the advantage from ph close to 8.5 at ph 9.5 the performance is not that far from the best These results underline that, in terms of temperature and ph of the washing bath, ε-phthalimido-peroxy-hexanoic acid acts best in milder conditions as compared to the two components bleaching systems. It also outperforms in alkaline conditions (ph = 9.5) that could comply with the other detergency requirements (fat removal, etc.).

10 EURECO 10 Colours and fibres damage evaluation The low aggressiveness of PAP to colours and fibres is also a very important property. Some comparisons have been carried out with the persalt + TAED combination at 25 C, testing cotton fabrics coloured with different dyes. The results after 30 and respectively 40 washing cycles are reported in figure 3-4 and figure Persalt/TAED PAP Dispersed Reactive Reactive Reactive Direct Blue Trichromat Trichromat Crimson Red Figure 3-4: Dye fading on coloured cotton after 40 wash cycles at 25 C Delta E Delta PSI Persalt/TAED PAP Dispersed Reactive Reactive Reactive Direct Blue Trichromat Trichromat Crimson Red Figure 3-5: Cotton fabric resistance after 30 wash cycles at 25 C Limits of the Experimental Error As far as the fabric resistance is concerned, PAP and activated persalt give a globally equivalent performance; in most cases the damage is close or below the limit of the experimental error. In the case of dye fading, the situation is practically the same. Disregarding the single results, an averaged conclusion is that there is no appreciable difference between the two bleaching systems, so that PAP is as safe to colours and fibres as persalt + TAED.

11 TM Bleaching Efficiency 11 FABRIC DAMAGE (%) TAED + PCS Boosters PAP 0 yellow blue pink brown violet light blue Figure 3-6: Cotton fabric resistance after 25 wash cycles at 60 C Low wearing of textiles Textiles lifespan can last even two times longer in comparison with Chlorine bleaches. REM-pictures below show the damage to fibres after 25 washes: PROCESS with PAP@50 C PROCESS with HYPO@85 C Figure 3-7: textile damage PAP vs. chlorine bleach (pictures by: Solvay)

12 EURECO 12 PAP compatibility with enzymes It is reported in literature that normally, organic peracids negatively interact with enzyme in the washing bath: due to their strong oxidative potential, peracids destroy the enzyme structure and consequently its detergent effect. In turn this critical point has been evaluated too, by testing a heavy duty powder composition containing PAP with and without enzyme, on different enzyme-sensitive stains. Particularly, two types of enzymes for detergent powders have been considered: a traditional enzymes and enzymes especially resistant to strong oxidisers. The results are displaced in figure 3-8 and show that: Reflectancy Values (%) HD Detergent + PAP HD Detergent + PAP + Enzyme A HD Detergent + PAP + Enzyme B A = Conventional B = Resistant to Oxidisers 45 wfk pre agged egg 164 wfk pigment/oil/milk wfk pigment/starch Figure 3-8: PAP compatibility with enzymes In all cases, the presence of enzymes only improves the stain removal, demonstrating that there is no negative interaction between PAP and enzymes; the use of specially protected enzymes does not give appreciable advantage and is, therefore, non necessary with PAP; traditional enzymes for detergent are completely compatible with PAP. The milder conditions at which PAP shows its best bleaching performance point out that PAP can be a suitable bleaching agent for light duty/hand washing detergents. The effect of the introduction of PAP into a light duty detergent is evident from the figure 3-9. The addition of a bleaching agent leads, as expected, to a much higher level of the bleachable stain removal, strongly increasing the overall detergent performance. Due to its mildness, PAP can be advantageously used in wool washing.

13 TM Bleaching Efficiency 13 Reflectancy Values (%) HD: Commercial Heavy Duty Detergent LD: Commercial Light Duty Detergent LD (bleach): LD + 15 % PCS + 5 % TAED LD (PAP): LD + 7 % PAP LD (bleach) HD LD HD LD T = 30 C LD (PAP) T = 40 C LD (bleach) LD (PAP) HD LD Red wine (Empa) Tea (Wfk) Tea (Röhm) Figure 3-9: Bleaching effect of PAP in light duty detergent T = 60 C LD (bleach) LD (PAP)

14 EURECO 14 Disinfektion Trends of washing It is a matter of fact that temperatures of textile washing in washing machines are gradually decreasing, particularly in Europe. Starting from the very high temperatures usually used for washing in former times (> 80 C), in the last decades the average washing temperatures dropped to roughly 60 C and the trend points to even lower temperatures. This change has many reasons, for example people wash more frequently garments less soiled, most fabrics are coloured and more delicate requiring mild washing conditions, and because low temperature washing leads to longer lasting of fabrics and allows for remarkable energy saving, etc. In order to guarantee the washing performance in spite of lower temperatures, great effort has been made to develop formulations containing new components that are increasingly efficient. The state of the art is that now good performances can be achieved at washing temperatures in the range of 60 C, complying with the habits and requirements of the eighties and early nineties but not fully in line with the average washing temperature approaching 40 C, with a motivated tendency to 30 C and lower today. Avarage washing temperature ( C) Figure 4-1: Trend of washing temperature One of the main problems arising from the process of lowering the washing temperature is related to hygiene. Indeed, it is well known that a good removal of microorganisms is guaranteed at a very high washing temperature (> 80 C) or by the combination of milder temperatures with the presence of effective anti-germs. Actually, a sufficient sanitization is achievable at 60 C with the use of activated persalts (persalt + TAED), but this system is not as well effective when the washing temperature is below that value. So, the detergents available today, based on the persalt + TAED combination, cannot ensure a good hygienic performance at low washing temperatures. This points out the risk of laundry that looks clean but is not sanitized; the consequences are well known to every housewife. The microorganisms are not visible, but their presence is revealed by some drawbacks like bad odours, spots of moulds, etc., which are quite perceivable.

15 TM Disinfektion 15 RESIDUAL BACTERICIDAL LOAD (%) HDW with PAP HAND Washing HDW with ACTIVATED Persaltes LIGHT Duty Washing HEAVY Duty Washing Figure 4-2: Residual bacterial load after washing at different temperatures Due to the fact that common surfactants per se are not strong enough to eliminate all germs, the hygienic problem of laundry washed at low temperatures in washing machines is practically the same for textile cleaned by hand or for delicate fibres. The common factor is that at low washing temperatures either for choice (washing machine) or for necessity (delicates, hand washing), a problem of hygiene arises; at a time when the need for hygiene is strongly increasing! 1,E + 08 Germ: Candida Albicans Exposure time: 45 min Number of Germs 1,E ,E ,E ,E ,E + 03 STD (no bleach) STD + 10 % PS STD + 7 % PAP Figure 4-3: Sanitizing effect of PAP in washing liquor at 40 C

16 EURECO 16 EURECO registration in the BPD positive list Despite its chemical reactivity, solid phase PAP shows a definitive intrinsic stability useful for processing its crystals into a wide range of products, from the liquid EURECO LX grades to the solid EURECO WM1, which systematically overcome many transportation restrictions relevant to this class of products. As a New Chemical, ε-phthalimido-peroxyhexanoic-acid (known as PAP) has been assigned an ELINCS number. PAP was registered at level II of ELINCS with the number and is registered and accepted within the BPD positive list. PAP has already been taken into account for its biocidal properties by major market players in the field of development and marketing of I&I laundry specialties that achieved the qualification from the Robert Koch Institute. In such products as well as in those commercially available from other leading companies, the presence of PAP is considered most important not only for providing the expected disinfection but also in coupling additional features like: Saving energy through low temperature process Saving investment through shorter cycles for washing Saving rinsing water through a mild ph in the process Saving costs through longer life of the textiles Easiness of dosing Safety and appeal for workers Powerful bleach and moderate anti-scale effects Environmentally friendly profile PAP is registered in the list of active ingredients of the BPD with relevance to the following product types: PT1 PT2 PT3 PT4 Human hygiene biocidal products Private area and public health area disinfectants and other biocidal products Veterinary hygiene biocidal products Food and feed area disinfectants For disinfection details, please refer to Appendix.

17 TM Usage in detergent 17 Usage of EURECO in detergent Grades for I&I EURECO LX10/LX17/LX20 EURECO LX10, LX17 and LX20 are white milky aqueous suspensions of PAP crystals, suitable for delivering high PAP level in total safety. EURECO LX10 contains 10 %, LX17 contains 17 % and LX20 contains 20 % of active PAP. The crystals of PAP are micronized through a proprietary technology patented by Solvay, thus allowing quick dispersion and dissolution. Performance: High bleach efficiency Wide disinfection Processing: Bleach at mild ph Low dosage of alkalis Savings: Low wearing out of textiles Low energy consumption Low rinsing water Low waste water treatment Safety: Ease of use for non professional workers Low risk for the company The moderate viscosity is designed to comply with the technical requirement of the automated dosage system installed on the tunnel industrial laundries as well as on OPL (On Premises Laundries).

18 EURECO 18 Washing conditions: tap water; T = 55 C; t = 30 minutes Degree of whiteness (%) Soiled linen = 20 g/l; NO PAP Soiled linen = 20 g/l; EURECO TM LX17 = 2 g/l Soiled linen = 50 g/l; EURECO TM LX17 = 2 g/l 60 red pepper red wine fruit juice tea Figure 5-1: Performance: High bleach efficiency effect of 340 mg/l of PAP EURCEO LX17 is able to maintain the original soft touch of textiles for longer time. Textiles washed with EURECO LX17 have no bad smell. EURECO LX17 (17 % PAP) in industrial laundry removal of microorganisms by standard washing cycle: T = 40 C - t = 15 min - ph = PAP concentration = 800 ppm MICRORGANISMS ABATEMENT Enterococcus FAECIUM > 10 7 Escherichia COLI > 10 7 Pseudomonas AERUGINOSA > 10 7 Staphylococcus AUREUS > 10 7 Aspergillus NIGER > 10 7 Candida ALBICANS > 10 7 Mycobacterium TERRAE > 10 7

19 TM Usage in detergent 19 The dosage of EURECO LX17 for bleaching may range from 1 to 14 g/litre of washing liquor, depending on the step of application, the level of dirt and the required performance. An example of dosage is reported in the following table: Dosage (a textile to bath ratio 1:4 is considered) Use in the main wash EURECO LX17 g/kg textile EURECO LX17 g/litre of bath Use in the rinsing stage EURECO EURECO LX17 g/kg LX17 g/litre textile of bath Low stained fabrics Normal stained fabrics Heavily stained fabrics Note: EURECO LX17 should not be used for bleaching silk, polyamide or elastomeric fabrics. Grades for consumers EURECO LX5 Liquid preparation (5 % active PAP) is consumer-tailored for the mass market and I&I, of high performance and stability, also suitable for spraying applications. % R Dosage: LD Liquid Detergent = 12 g/l LDD + EURECO TM LX 5 % PAP (2g/l) LDD + H 2 O 2 -based booster (5g/l) Light Duty Detergent wine tea grass egg coca grafit oil Figure 5-2: Light duty washing: overall performance at T = 20 C, t = 30 min

20 EURECO HDD + EURECO TM LX5 % PAP (5 g/l) HDD + PSC/TAED booster (5 g/l) Heavy Duty Detergent 70 % R wine tea grass egg coca grafit oil Figure 5-3: Heavy duty washing: overall performance at T = 40 C, t = 30 min Dosage for hand washing: mix 40 ml into 5 l water, pure or with detergent for coloured or delicate fibres, after washing rinse out with plenty of water. Allow to soak not longer than one hour. Dosage for machine washing: add 80 ml together with the usual amount of detergent into the washing machine and start the process immediately. Do not use a timer. Application: for textiles with skin contact, for example underwear, socks, nightwear, blouses, also suitable for wool for baby- and children-wear for wet and sweaty textiles with bad smell, like sportswear or sauna towel for hard surfaces like tiles, shower cubicles or kitchen work surface

21 TM Regulations 21 EURECO LX5V It is a water-based, human-safe carrier of PAP, designed for direct application as bleach booster for consumer and for I&I applications, as well as a biocidal product. Application: EURECO LX5V is specially formulated for use where high viscosity and wetting or mild detergency capacity is necessary. The performance of EURECO LX5V triggers off promptly even under mild conditions (low to moderate temperatures and ph). It is a pseudoplastic liquid which shows a prompt reduction of the viscosity by application of a shear stress. Regulations EURECO LX5 is not an ADR material EURECO LX5V is not an ADR material EURECO LX10 is not an ADR material EURECO LX17 is not an ADR material EURECO LX20 is not an ADR material Attention Attention Danger Danger Danger Eye Dam. 1 H319 Causes serious eye irritation Eye Dam. 1 H319 Causes serious eye irritation Eye Dam. 1 H318 Causes serious eye damage Eye Dam. 1 H318 Causes serious eye damage Eye Dam. 1 H318 Causes serious eye damage Packaging: all grades are available in 0,5 l bottles up to kg IBCs.

22 EURECO 22 Appendix BIOCIDAL ACTIVITY OF phthalimido peroxyhexanoic acid EU Test Protocol PAP mg/l AvOX mg/l Contact time min Product Type 1 EN 1040 Bactericidal activity (BASE ACTIVITY) Temperature C Staphylococcus Aureus ATCC Pseudomonas Aeruginosa ATCC EN 1276 Bactericidal activity (SUSPENSION TEST: 0.3% bovine albumin) Staphylococcus Aureus ATCC Pseudomonas Aeruginosa ATCC Enterococcus Hirae ATCC Escherichia Coli ATCC EN Fungicidal activity (SUSPENSION TEST: 0.3% bovine albumin) Candida Albicans ATCC Aspergillus niger ATCC EN Virucidal Activity (0.3% bovine albumin + 0.3% ram erythrocytes) poliovirus type adenovirus type poliovirus type adenovirus type EN WI 15 Mycobactericidal activity (SUSPENSION TEST: 0.3% bovine albumin) Mycobacterium Terrae Product Type 2 and 4 EN Bactericidal activity (SURFACE TEST: 0.03% bovine albumin) Staphylococcus Aureus ATCC Pseudomonas Aeruginosa ATCC Enterococcus Hirae ATCC Escherichia Coli ATCC

23 TM Appendix 23 BIOCIDAL ACTIVITY OF phthalimido peroxyhexanoic acid EU Test Protocol PAP mg/l AvOX mg/l Contact time min Product Type 2 and 4 continued from page 22 Temperature C EN Fungicidal activity (SURFACE TEST: 0.3% bovine albumin) Candida Albicans ATCC EN Fungicidal activity (SURFACE TEST: 0.03% bovine albumin) Candida Albicans ATCC Penicillium Verrucosum var. Cyclopium CIP Product Type 3 EN 1656 Bactericidal activity (SUSPENSION TEST: 0.3% bovine albumin) Staphylococcus Aureus ATCC Pseudomonas Aeruginosa ATCC Enterococcus Hirae ATCC Proteus Vulgaris ATCC EN 1656 Bactericidal activity (SUSPENSION TEST: 1% Reconstituted Milk) Staphylococcus Aureus ATCC Pseudomonas Aeruginosa ATCC Enterococcus Hirae ATCC Proteus Vulgaris ATCC EN 1656 Bactericidal activity (SURFACE TEST: 0.03% bovine albumin) Staphylococcus Aureus ATCC Pseudomonas Aeruginosa ATCC Enterococcus Hirae ATCC Proteus Vulgaris ATCC EN 1657 Fungicidal activity (SUSPENSION TEST: 0.3% bovine albumin) Candida Albicans ATCC EN 1657 Fungicidal activity (SUSPENSION TEST: 1% Reconstituted Milk) Candida Albicans ATCC EN Fungicidal activity (SURFACE TEST: 0.03% bovine albumin) Candida Albicans ATCC

24 04/13 HARKE CleanCare a Business Unit of the HARKE Chemicals GmbH Xantener Straße Mülheim an der Ruhr Germany Internet Thorsten Pohl Senior Product Manager Phone +49 (0) Fax +49 (0) po@harke.com Karolin Rouette Technical Sales Manager Phone +49 (0) Fax +49 (0) kr@harke.com No guarantee, warranty or representation is made, intended, or implied as to the correctness or sufficiency of any information, or as to the suitability of any chemical compounds for any particular use. Each user should conduct a sufficient investigation to establish the suitability of any product for his intended use. The information contained above are to the best of our knowledge.