ANALYSIS OF ALTERNATIVES - ECHA

ANALYSIS OF ALTERNATIVES

Substance Name: EC Number: CAS Number: Submitting Applicant: Use title: Use number:

Sodium dichromate (Na2Cr2O7) 234-190-3 7789-12-0 (Dihydrate) / 10588-01-9 (Anhydrous) Gruppo Colle s.r.l. Use of Sodium dichromate as mordant in wool dyeing 1

Report date 25/10/2016

The information in this document is the property of Gruppo Colle s.r.l.. It may not be copied without the express written consent of Gruppo Colle s.r.l.. The information is given in good faith based upon the latest information available to Gruppo Colle s.r.l..


25.09.2016 Use of Sodium dichromate as mordant in wool dyeing – Gruppo Colle s.r.l. 2

CONTENTS 1. SUMMARY ............................................................................................................................................................... 6 2. ANALYSIS OF SUBSTANCE FUNCTION...................................................................................................................... 6

2.1. Introduction .................................................................................................................................................... 6 2.2. General description of the process of wool dyeing ........................................................................................ 7 2.3. Factors affecting the dyeing of protein fibers ................................................................................................ 11 2.4. Annual Tonnage .............................................................................................................................................. 14

3. IDENTIFICATION OF POSSIBLE ALTERNATIVES ........................................................................................................ 14 3.1. Families of dyes for wool dyeing and related problems ................................................................................. 14 3.2. Identification of alternatives .......................................................................................................................... 15

3.2.1. LANASOL® Reactive Dyes .................................................................................................................... 16 3.2.2. Realan EHF® Reactive Dyes ................................................................................................................. 17 3.2.3. Sulphur Black 001 ................................................................................................................................ 18 3.2.4. Others .................................................................................................................................................. 19 3.2.5. Data searches ...................................................................................................................................... 20 3.2.6. Consultations ....................................................................................................................................... 20

4. SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES................................................................................. 20 4.1. Substance ID and properties........................................................................................................................... 25 4.2. Reduction of overall risk due to transition to the alternative ........................................................................ 26 4.3. Economic feasibility ........................................................................................................................................ 26

4.3.1. Cost of Raw Materials per formulation ............................................................................................... 27 4.3.2. Process costs ....................................................................................................................................... 27 4.3.3. Research & implementation of the Reacive Dyes process .................................................................. 29 4.3.4. Plant modification investment ............................................................................................................ 29 4.3.5. Availability ........................................................................................................................................... 30 4.3.6. Customers approval ............................................................................................................................ 30

5. OVERALL CONCLUSIONS ON SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES FOR USE .................... 30 5.1. Technical performance ................................................................................................................................... 33 5.2. Human health aspects .................................................................................................................................... 33 5.3. Environmental aspects ................................................................................................................................... 34 5.4. Economical aspects ......................................................................................................................................... 34 5.5. List of actions .................................................................................................................................................. 34

ANNEX I – REFERENCES ................................................................................................................................................. 36 ANNEX II – JUSTIFICATIONS FOR CONFIDENTIALITY CLAIMS ........................................................................................ 37



Figures: Figure 1: Classification of animal fibers ........................................................................................................................ 7 Figure 2: End uses of wool in connection with the fiber diameter ............................................................................... 7 Figure 3: Wool usages in textile world.......................................................................................................................... 8 Figure 4: Composition of a wool fiber .......................................................................................................................... 9 Figure 5: Keratin structural form .................................................................................................................................. 10 Figure 6: Formation of the coordination complex ........................................................................................................ 12 Figure 7: Interaction example complex 1:1 dye/chrome/fiber .................................................................................... 13 Figure 8: Application characteristics for families of dyes ............................................................................................. 14

Tables: Table 1: List of alternatives indicated in SUBSPORT ..................................................................................................... 16 Table 2: Reactive Yellow 039 safety characteristics ..................................................................................................... 17 Table 3: Reactive Black 005 safety characteristics ........................................................................................................ 18





LIST OF ABBREVIATIONS

AfA Application for Authorisation AMD Alkali Metal Dispenser ATEX ATmosphères EXplosibles (1999/92/EG & 94/9/EG) AoA Analysis of Alternatives CAS Chemical Abstracts Service CBA Cost Benefit Analysis CLP Classification Labelling and Packaging (EC) 1272/2008 CMR Carcinogenic, Mutagenic or toxic to Reproduction CSR Chemical Safety Report DSD Dangerous Substance Directive 67/548/EEC DU Downstream User EC European Commission ECHA European Chemicals Agency EEA European Economic Area ES Exposure Scenario eSDS Extended Safety Data Sheet ERC Environmental Release Category EU European Union FPD Flat-Panel Detector GC-MS Gas Chromatography – Mass Spectrum II Image Intensifier LAD Latest Application Date LE Legal entity LoA Letter of Access LR Lead Registrant MOS Margin of Safety OC Operational Condition NVD Night Vision Device PPE Personal Protection Equipment PPM Parts Per Million PV Present Value R&D Research and Development RAC Risk Assessment Committee RCR Risk Characterisation Ratio REACH Registration, Evaluation, Authorisation & restriction of Chemicals RMM Risk Management Measures RPE Respiratory Protective Equipment SCOEL Scientific Committee for Occupational Exposure Limits SVHC Substance of Very High Concern SEA Socio Economic Analysis SOP Standard Operating Procedures VOC Volatile Organic Compounds WIPO World Intellectual Property Organisation WTP Willingness To Pay WWTP Waste Water Treatment Plant



1. SUMMARY

The Applicant, Gruppo Colle s.r.l. is one of the most important leader companies in fibre dyeing for textile in Italy. It has been working for over 60 years to improve the quality of the dyeing process paying much attention to the technological research and to the constant training of its employees. It is in Italy one of the main producer of dyed wool and uses Cr(VI) salts in connection with mordant dyes since 30 years. Due to the well known hazard connected to the Cr(VI) salts the whole production process has always been conducted in very strictly controlled conditions to reduce emissions and exposure at the minimum. In the meantime Gruppo Colle s.r.l. kept in evaluating and developing potential alternatives in order to substitute dichromate salts into the production process, but the research still don’t reach an acceptable point at all levels, neither for the Applicant or the competitors. In the following report all potential considered alternatives have been described and the analysis has highlighted that there is no indication of an existing valid alternative up to now that can be used for complete substitution of Cr(VI) salts and, where possible, this substitution will take time. A prevision of a minimum of 6 to a maximum of 10 years has been estimated to find a valid implementation of the existing substitution and to find a chemical substitution or technology where the first is actually not working properly.

2. ANALYSIS OF SUBSTANCE FUNCTION

2.1. Introduction

Chrome based dyeing that requires the use of sodium dichromate, plays an important role in Gruppo Colle dyeing processes. The results obtained, in terms of fastness and performances, cannot be reached by no other type of dye present on the market. Although some manufacturers are trying to propose alternatives, currently no class of dyes exists that can compete either for quality or for performance nor for benefits at the process level. Chrome based dyes guarantee a depth of tone and intensity that cannot be reached with other dye molecules. Reactive dyes, closest to a qualitative performance in dark tones (es. navy blue or black), do not succeed to be competitive in all aspects. In addition, the reactive dyes have a much higher cost with a difference of at least 1.40 € per kg of dyed fiber, this parameter is often daunting for orders from the Applicant customers. Dark tones are especially popular in the world of men's fashion for keratin fibers and cover a large share of the market in particular in the production of suits, jackets and knitwear. In this respect, Gruppo Colle, to respond to the needs and to increasingly stringent customer requirements, considers the use of chrome processes a crucial phase of its production process. In addition to the colour properties and to the good wet fastness, the chrome based processes lead advantages linked to energy and economic saving and environment protection. These processes require shorter processing times and fewer temperature ramps: this means a great energy saving level that is near to a 40 % less in comparison with the other dyeing methods (reactive dyes). Even the water consumption is drastically reduced if compared to dyeing performed with other dyes, for example with reactive dyes, up to 30-35 % less. In fact the chrome base dyeing doesn’t require so many rinsing and soaping (cleanups) steps that are mandatory when reactive dyes are used. The economic benefits are also related to a greater productivity of the plant: a considerable reduction of the required time is obtained, about 100 minutes less considering the complete cycle, which allows in a work shift to perform a greater number of dyeing.



2.2. General description of the process of wool dyeing

Coloration of protein fibers is a very complex domain (Sawatwarakul, 2014). There are many variables that can affect the outcome of dyeing. Indeed it is quite complicated to get the right colour in the first dyeing attempt. Determining the root causes of a given problem is even more challenging. In the era of energy saving, water saving and eco-friendly processing it is tough to maintain the high expected quality of products and reduce the cost of the process. The interest in the scientific community pertaining to research on protein fibers has been decreasing significantly over the recent years, while the study of synthetic polymers has advanced tremendously. Therefore, regrettably, a lack of up to date literature pertaining to the coloration of protein fibers, and especially on the subject of the recommended solutions and procedures to overcome the associated problems, is apparent. The classification of “protein” fibers is shown in Figure 1:

Figure 1: Classification of animal fibers

Wool is processed into a wide range of end products. End use of wool are determined by the main characteristics of fibers, including diameter, length, strength, colour and hand, lustre, bulk, presence of impurities, and level of felting. An example of end use based on fiber diameter is as shown in Figure 2:

Figure 2: End uses of wool in connection with the fiber diameter in m



Wool is a globally traded commodity and its market diversity is vast and expanding including sections such as fashion, active wear, flooring and interiors, aviation, architecture, manufacturing, medical use, and protective apparel etc. as shown in Figure 3:

Figure 3: Wool usages in textile world

Wool is used widely in three main sectors: apparel, interior textiles and technical textiles. In the apparel sector wool is used for the production of suits, jackets, pullovers, coats, socks, sportswear, skiwear, active wear, thermal underwear, scarves, gloves, hats, waterproof fabrics, shoes, children wear, hand knitting, kilts, etc. In the interior textiles sector wool is used in duvets, mattresses, pillows, blankets, upholstery, tapestries, lamp covers, chairs, rugs, bedspreads, sofas, felts, carpets, tablecloths, wall coverings, futons, etc. Wool has also been used in the technical textiles sector, for example in aircraft interiors, air-conditioning, bandages, fireproof wear, filtration, police uniforms, military uniforms, thermal insulation, second skin injury prevention, sound insulation, sound vibration control, piano felts, automotive composites, roof insulation, dust and chemical odour filters, billiard covers and tennis balls. The inherent properties of wool such as its excellent insulating properties, resilience to applied pressure, wicking moisture, as well as its naturally non-allergenic nature makes it suitable for use in medical applications Wool represents a large class of animal hairs, which share a common chemistry, structure, and morphology. The high sulphur content in wool comes from the high cysteine content of these fibers. Wool fiber diameters can range from 11 μm (fine Australian Merino) to 100 μm (sheep of northern hemisphere) respectively. Under the microscope, the wool fiber appears as a solid rod with its surface covered with scales. The scales



project slightly from the stem of the fiber and point slightly outwards toward the tip. Morphologically, the fibers are composed of a cortex and a cuticle, and may also contain a section known as medulla (in coarse wool only). Each of these is further subdivided by tissue differentiation as shown in Figure 4

Figure 4: Composition of a wool fiber

The cuticle is formed of four layers; the outermost is the epicuticle, a thin, water-repellent membrane, then come the a-layer, the exocuticle, and the endocuticle. The epicuticle has tiny pores which enable water to penetrate into the internal structure of the fiber. The cuticular cells overlap and protrude for about one-third of their length, their outermost ends being directed towards the tip of the fiber. This arrangement of cuticle cells on the fiber surface creates directional frictional effect which is responsible for the ability to felt wool. The surface of wool fibers is made up of the epicuticle and a small lipid component around 0.05% consisting of the region that extends to the fiber surface. The thickness of the lipid layer on the fiber surface is approximately 0.9 nm. The cortex is the cellular portion inside the cuticular cell layers and it contains cortical cells, each of which surrounded by the remains of the cell membrane complex. The tensile strength, elastic properties, and the natural colour of wool are determined mainly by the nature of the cortical cells]. The fiber is composed of protein “keratin” which is a complex polymer with an empirical formula C72H112N18O12 -amino acids. The nature and molecular weight of the side chains determine the physical and chemical properties of wool. In the unstressed state, the keratin polymer has a helical or spiral configuration, known as the α-helix

as shown in Figure 8. Two -helices are joined together by hydrophobic bonds into a coiled-coil structure of 50 nm length. In water, under the influence of applied external stress, the wool fiber will stretch and this will straighten or unfold the keratin polymer chains. The fully-unfolded configuration of the keratin is known as β-keratin. On removal of stress, the β-form will return to the original α-keratin structural form.



Figure 5: Keratin structural form

Linkages and bonds in wool include the following:

1. Hydrogen bonds 2. Salt linkage or bridge 3. Cystine linkage

Protein fibers can be dyed in four forms; fiber (“loose stock” or “top” dyeing), yarn (“hank” or “package” dyeing), fabric (“piece dyeing”), and in garment form. Wools obtained from sheep are mostly dyed in fiber and yarn form. Dyeing machines with low fiber-liquor interchange require dyes with high migration properties (i.e. excellent levelness). For example, for hank dyeing in yarn form or piece dyeing in the winch, leveling acid dyes are used but these dyes tend to exhibit poor wet-fastness properties. For machines with excellent fiber-liquor interchange, for example in package dyeing and soft-flow jet machines for piece dyeing, dyes with lower migration rates are selected because they have good wet fastness properties. Continuous or semi-continuous processes are not common practice in wool dyeing Raw wool needs to be scoured to remove impurities prior to dyeing. In spun wool processing loose wool may be dyed right away, but worsted wools are not dyed until after combing. Dyes selected for dyeing fibers must have good fastness to wet treatments because the spun yarn from these fibers will need to undergo further processing, such as scouring, milling, or potting. Dyes with good wet fastness generally exhibit inferior levelling properties and thus it is difficult to achieve uniformity of shade; however, levelness of shade is less critical in fiber dyeing than in yarn and piece dyeing because any minor non-uniformity is eliminated in carding or gilling steps which result in a thorough mixing of the dyed fibers. Shade matching is also easier to achieve in loose-fiber dyeing. Reasons to dye wool at this stage include production of large lots of yarn with good shade uniformity, mixing shades, high wet fastness properties, and products based on fiber blends. Disadvantages include potential fiber damage during the dyeing process which reduces the efficiency of spinning in comparison with un-dyed wool.



2.3. Factors affecting the dyeing of protein fibers

The dyeing process is complicated. A list of factors that influence the dyeing of protein fibers is shown in the following:

Fiber origin

Yarn type

Fabric structure

Water quality

Yarn/fabric preparation

Dye selection

Temperature

Time

pH

Fabric moving speed

Load capacity

Liquor ratio

Heating and cooling rate

Dosing of dyes and auxiliaries

Dye solution flow rate and circulation time

Pad pressure The objective of dyeing is to produce uniformly-coloured substrates that match a pre-selected colour. As the production of dyed protein goods involves many processes, many variables can affect the appearance of final shade including texture, construction of the substrate (chemical and physical), pre-treatment processes prior to dyeing, and post-treatment processes after the dyeing process.

Complexation chromium - dyes and description of the chelation reaction. Some acid dyes are able to combine with the chromium on the surface of the fiber giving rise to macromolecular complexes that become less soluble in aqueous solutions and which involve the formation of a network of fiber-dye interactions which greatly increases the force with which the dyes are bound to the fiber. These molecules, in addition to ensuring considerable qualitative standards, color depth and tone cannot be reached with other classes of dyes, require dyeing processes not particularly complex and therefore advantageous from an energy point of view. The correct use of chemical compounds together with the refining of the processing parameters allows to significantly reducing the environmental impact.



Figure 6: Formation of the coordination complex

In recent decades the chemical evolution has allowed the development of more appropriate molecular structures that are capable of quickly forming coordination complexes with the addition of particular chemical groups. In order to obtain very intense shades on wool, in intense blue to black colors, chrome dyes have found widespread use as they give intense shades combined with exceptional wet strength and excellent resistance to light. The role of this class of dyes in the textile industry is of primary importance, it was estimated that the dyes chrome cover about 20 % of the total market of dyeing keratinous animal fibers, primarily for black dye and navy blue. Currently, some manufacturers are attempting to replace the chromium with reactive dyes which, however, fail to provide the same characteristics and performance such as:

The depth of tone;

Fastness to wet;

The coverage of dead hair; Despite numerous studies carried out by various research groups, the exact chemical mechanism that takes place during the chromating process is not completely clear. It seems that the dye molecules act as ligands by forming coordination complexes with trivalent cations of chromium (Cr(III)). This reaction taking place in the vicinity of the surface of the fiber generates an increase of the chemical and physical performance, quality and an improvement in the appearance of the dye. Crucial point of the process is represented by its reaction with the metal which results in a color change and the color of the bath during the reaction of complexation. A fundamental aspect for the success of the reaction is represented by the shape of the metallic chemical species that is introduced into the dyeing bath: chromium (III) has a positive charge and this contributes to its low substantivity towards the amino groups present on the macromolecular chain of the keratin; during the stages of processing carried out in an acidic environment, they are protonated to NH3

+ generating a natural electrostatic repulsion. For this reason, the choice of the chemical form of chromium falls on the use of hexavalent oxidation state that has an anionic charge (Cr(VI)), used commonly in the form of sodium or potassium salt and specifically as dichromate. The species present in the aqueous solution of K2Cr2O7 vary in function of pH. The anions dichromate containing Cr(VI) are immediately absorbed on the protonated amine groups in the substrate. The amount of adsorbed chromium from wool depends on several factors such as pH, the temperature and the presence of inorganic salts (Na2SO4) , that can be used



to accelerate the absorption of chromium. The dyeing bath which the chromate probably contains a variety of anionic species of Cr: dichromate and chromate ions. This further complicates the process and makes not entirely clear what is the identification of the precise nature of the chemical species absorbed by the keratin fibers. In some publications it has been suggested that the HCrO4

- ion, which is formed by the hydrolysis of the dichromate, can be the absorbed species. However, such chemical species is not the predominant if we consider the operating conditions and the pH. During the chromate reaction, hexavalent Cr(VI) anions are adsorbed on the protonated amine groups of the fiber by means of a Freundlich isotherm. At the same time the anions Cr(VI) are reduced by cysteine present on the wool fiber to the trivalent form, cations of Cr(III), which are complexed by the dye molecules that are already adhering to the surface of the fiber. Although this reduction process, which is dependent on the temperature, and pH, is not well understood, it is believed that Cr(VI) is reduced to Cr(III) through the intermediate generation of species such as CrIV and CrII. Such a process that occurs with consequent release of protons is corroborated by the pH reduction which occurs during the chromating process. The literature shows that the reduction of chromium (VI) to chromium (III) on wool easily occurs at temperatures equal to or higher than 60 °C. This process of reduction was attributed to the disulfide bonds present in cysteine. Other amino acids may intervene in the reaction of oxidation-reduction such as tyrosine and lysine, however, their action is shown only at pH around 7, and these pH values, high, are not normally encountered in the dyeing of chrome. It must therefore be concluded that the direct reduction of chromium (VI) by the cysteine is the main route of chromium generation (III) in the dyeing process for chromate. The nature of the complex that is formed depends on the operating conditions, the pH of the solution and the solubility of the dye. Such complexes, of important molecular sizes, are tightly bound to the fiber.

Chromium(VI) ↓

Oxidation of cystine Chromium(VI)

↓ Oxidation of cystine,

methionine and tyrosine Chromium(II) (IV)

↓ Wool-CO2H

Wool-COO Cr(II)(IV) ↓

Rapid oxidation-reduction Wool-COO Cr(III)

Figure 7: Interaction example complex 1:1 dye/chrome/fiber



2.4. Annual Tonnage

Confidential average annual tonnage for use:

3. IDENTIFICATION OF POSSIBLE ALTERNATIVES

3.1. Families of dyes for wool dyeing and related problems

Studies have been performed for many years and efforts in finding possible alternatives for chromates. The alternatives have been evaluated according to different approaches, either chemical or technological. While fibres may be dyed with specific classes of dye in some cases they may result in damaging the material. For instance, in dyeing of wool or silk with sulphur, hot reactive and vat dyes some damage may occur due to application conditions. The highly alkaline pH maintained during dyeing at high temperature partially disintegrates protein fibers causing a reduction in tensile strength. Protein fibers including wool and silk have dye-sites that under acidic conditions become protonated (-NH3+) in their main polymer chain which are attractive to acid/metal complex dyes. Basic-dyeable sites can also be made on protein fibers under suitable conditions but basic dyes exhibit poor light fastness properties

Figure 8: Application characteristics for families of dyes

Acid dyes are mostly sulphonic or carboxylic acid salts which are applied from an acidic bath. The dye anion is the active colouring component in these molecules. Acid dyes possess affinity for protein fibers and form ionic bonds that retain the dye within the fiber. Acid levelling dyes: This class is suited for dyeing yarn and fabric where levelling is important, they exhibit moderate wash fastness but do not exhibit high fastness to either hand or machine washing because of their low molecular weight and high water solubility.



Acid milling dyes Acid milling dyes exhibit improved wet fastness. Their migration is lower than that of levelling dyes

Mordant dyes These may be subdivided into pre-mordant, metachrome, and afterchrome dyes. Mordanting with chromium produces dyes of high wet fastness and good light fastness. The after chrome process is the most widely used because it results in high wet fastness and best levelling properties.

1:1 Metal complex dyes This class of dye has good levelling properties in dyeing wool, nevertheless they are not good with washable wools because their wet fastness is not as good with modern detergents containing perborate. Exhaustion of 1:1 metal complex dyes from a neutral bath is not high and dyeing generate poor rubbing, milling, and light fastness properties. Strong acidic pH conditions damage wool, and because of the higher water solubility of the dyes containing -SO3H groups, dye exhaustion is poor; being salts of strong acids, these dyes have too little substantivity for the fiber.

1:2 Metal complex dyes They have low affinity under neutral conditions thus requiring more acid to achieve exhaustion, but possess the highest fastness to domestic washing Reactive dyes Reactive dyes produce very bright shades on wool with moderate to good light fastness (5-7) and good wash fastness (4-5). Affinity of reactive dye for wool is very high which can pose problems for the production of level shades. Non-uniform initial adsorption of dye on fiber must be avoided with addition of nonionic surfactants. Dye-fixing agents are only applied during the last wash to avoid staining and to improve wash fastness. Clearing is necessary to remove the unfixed dye. Due to their poor levelling properties, these dyes are especially suited for dyeing loose fibers. A specific class of reactive dye systems was developed which in dyes do not fix to wool fiber until the bath is raised to the boil or until the bath is made alkaline during an after-treatment to achieve improved levelness. Lewis (Lewis, 1992) proposed a two-stage method for dyeing wool with all types of reactive dyes whereby the initial level-dyeing period is carried out under acidic conditions, during which controlled dye–fiber reaction occurs; then, as soon as a bath temperature of 100°C is reached, the acid disappears from the system through a free radical decomposition reaction. Such a decomposition of the acid is advantageous in that it occurs in a progressive and levelled manner throughout the dye-bath and fiber mass. The neutralization of an acid bath using alkalis can lead to uneven results, due to unequal absorption of the alkali by the wool fiber. Trichloroacetic acid is a very strong acid capable of producing pH values below 2. It decomposes in water at about 100°C to give free radicals. Since the chloroform and carbon dioxide produced are volatile, they are rapidly removed from the dye-bath. The strong acidity of trichloroacetic acid is attributed to the combined inductive effect of the three chlorine atoms (which gives almost complete dissociation of the proton from the carboxylic acid group)

3.2. Identification of alternatives

A reference document for an overview of alternatives can be found in the SUBSPORT (SUBstitution PORTal). SUBSPORT is a LIFE+ Project finance by BAuA – Federal Institute for Occupational Safety and Health, Germany and the Federal Ministry of Agriculture, Forestry, Environment and Water Management, Austria.

The overall expected result of the project was the realisation of a web portal containing information on substituting hazardous substances by safer alternatives. The goal was to develop an internet portal, which constitutes a state-of-the-art resource on safer alternatives to the use of hazardous chemicals that provide information on alternative substances and technologies as well as tools and guidance for substance evaluation and substitution management. The portal should support companies in fulfilling substitution requirements of EU legislation, such as those under the REACH authorisation procedure, the Water Framework Directive or the Chemical Agents Directive and provide interested parties with information and



tools to facilitate effective substitution of hazardous substances. A number of 18 activities/tasks were planned within the 3 years of the project and within the 18 activities, in April 2015 was published a report on Cromium VI in dyeing process. Within the report the following alternatives are indicated:

Sodium/potassium dichromate alternatives in textile dyeing: 1. Potassium aluminum sulphate 10043-67-1

2. Stannous chloride 7772-99-8

3. Copper sulphate 7758-98-7

4. Iron (II) sulphate 7720-78-7

5. Sulfated castor oil (Turkish red oil) 8002-33-3

6. Disodium 4-[4-[[5-[(2-bromo-1-oxoallyl)amino]-2-sulphonatophenyl]azo]-4,5-dihydro-3-methyl-5-oxo-1H-pyrazol-1-yl]-2,5-dichlorobenzenesulphonate (LANASOL 4G) – Reactive Yellow 039

70247-70-0

7. Tetrasodium 4-amino-5-hydroxy-3,6-bis[[4-[[2-(sulphonatooxy)ethyl]sulphonyl]phenyl]azo]naphthalene-2,7-disulphonate – Reactive Black 005

17095-24-8

Table 1: List of alternatives indicated in SUBSPORT

The first 5 are just applied in the dyeing of textile with natural dyes (Samanta, 2011) and are out of the scope of this evaluation. The last two identified chemicals are the main representative of two different families of Reactive dyes for wool, the family of α-bromoacrylamide Reactive Dyes (LANASOL®) and vinylsulpho derivatives Reactive Dyes (Realan EHF®). Their updated health properties have been reported in the ECHA website in the disseminated Registration dossier

3.2.1. LANASOL® Reactive Dyes

Reactive Yellow 039 (CAS 70247-70-0)

Hazards Properties Source of information

Physical Hazards

Explosivity Dust explosion risk ECHA database

Flammability Not flammable ECHA database

Oxidizing No Oxidising properties ECHA database

Human Health Hazards

Acute toxicity

Highly toxic Not toxic ECHA database

Skin or eye corrosion / irritation Not skin or eye irritant/corrosive ECHA database

Chronic toxicity

Carcinogenicity Not carcinogenic ECHA database

Mutagenicity Not mutagenic ECHA database

Reproductive toxicity (including developmental toxicity)

Not toxic for reproduction ECHA database

Endocrine disruption Not listed OECD, EU Endocrine disruptor database, SIN list

Respiratory or skin sensitization Skin and Resp sens. 1 (H317, H334) Asthmagen (ARs) - sensitizer-induced

ECHA database AOEC Exposure Codes - Asthmagen List

Neurotoxicity Not listed Vela et al.



Immune system toxicity Data lacking -

Systemic Toxicity Not toxic ECHA database

Toxic metabolites Data lacking -

Environmental hazards

Acute/chronic aquatic toxicity Not toxic ECHA database

Bioaccumulation Not bioaccumulative ECHA database

Persistence Persistent ECHA database

Greenhouse gas formation potential

Not listed IPCC

Ozone-depletion potential Not listed SCORECARD

Monitoring – has the substance been found in human or environmental samples?

Data lacking -

Table 2: Reactive Yellow 039 safety characteristics

During the 80th IWTO Congress - Hangzhou, China 2011 the Huntsman Textile Effects presented the result of a project that was running during the previous 10 years. They presented in fact an innovative technology that allowed replacement of chrome dyes with sustainable products, and a new range of metal-free reactive dyes for wool, LANASOL® CE, first appeared on the market. These dyes have very good fiber levelness, high fastness, including wet fastness, and reproducibility. Furthermore, the dyes ensure that the wool fiber is fully preserved and leave the finished article with a pleasant handle. The range has been designed for exhaust dyeing of untreated, chlorinated and machine-washable wool at all processing stages, especially loose stock, slubbing and yarn. The dyes are also suitable for coloured discharge printing of wool. LANASOL® dyes contain α-bromoacrylamide reactive groups that react with the amino groups of wool fiber and provide wet fastness to meet the machine-washable wool requirements of the Australian Wool Innovation (AWI) Woolmark standard. LANASOL® dyes have good levelling properties when used with ALBEGAL® B (substituted alkylamine polyglycol ethers with amphoteric properties) in slightly acidic conditions. A wide shade range can be covered with the trichromatic dyes LANASOL® Yellow 4G, Red 6G and Blue 3G. Compared to the previous studied alternatives, those dyes mantain fiber preservation as well as the chrome dyes. On the other side, in practice, it is very difficult to find on the market products free of impurities like p-chloro anlyline and 2-naphtylamine, two amines listed between the EU banned aromatic amines. Since August 2012, the new standard EN 14362-1:2012 Textiles - Methods for determination of certain aromatic amines derived from azo colorants - Part 1: Detection of the use of certain azo colorants accessible with and without extracting the fibres is effective. It had been officially approved by the European Committee for Standardization (CEN) and supersedes the test standards EN 14362-1: 2003 and EN 14362-2: 2003. The standard describes a procedure to detect EU banned aromatic amines derived from azo colorants in textile fibres, including natural, man-made, regenerated, and blended fibres. The standard is also relevant for all coloured textiles, e.g. dyed, printed, and coated textiles. Gruppo Colle is regularly applying this standard as regular quality control procedure on the raw materials

3.2.2. Realan EHF® Reactive Dyes

Reactive Black 005 (17095-24-8)

Hazards Properties Source of information

Physical Hazards

Explosivity Not explosive ECHA database

Flammability Not flammable ECHA database

Oxidizing Not oxidizing ECHA database

Other properties of reactivity Stable ECHA database

Human Health Hazards

https://en.wikipedia.org/wiki/Azo_compound



Acute toxicity

Highly toxic Not toxic ECHA database

Skin or eye corrosion / irritation Not Skin or Eye ittirant/corrosive ECHA database

Chronic toxicity

Carcinogenicity Not carcinogenic ECHA database, IARC

Mutagenicity Not mutagenic ECHA database

Reproductive toxicity (including developmental toxicity)

Not toxic for reproduction ECHA database

Endocrine disruption Not listed OECD, EU Endocrine disruptor database, SIN list

Respiratory or skin sensitization Skin and Resp sens. 1 (H317, H334)

ECHA database, not supported by data

Neurotoxicity Not listed Vela et al.

Immune system toxicity Data lacking -

Systemic Toxicity Not toxic ECHA database

Toxic metabolites Data lacking -

Environmental hazards

Acute/chronic aquatic toxicity Not toxic ECHA database

Bioaccumulation Not bioaccumulable ECHA database

Persistence Listed as persistent ECHA database

Greenhouse gas formation potential

Not listed IPCC

Ozone-depletion potential Not listed SCORECARD

Monitoring – has the substance been found in human or environmental samples?

Data lacking -

Table 3: Reactive Black 5 safety characteristics

While reactive dyes constitute one third of dyes used for cellulose an increasing amount of specifically-designed reactive dyes are used on wool and nylon. Lanasols (Huntsman) and Realan EHF (DyStar) appear to be the only ranges marketed specifically for wool. The dyes contain chemical groups that are capable of covalently binding with amino, thiol, and hydroxyl group in wool. Reactive dyes on protein substrates perform significantly better compared to cotton with lower associated environmental concerns. Poor dye fixation has been a longstanding problem with reactive dyes on cellulosic substrates; however, due to their high shade-reproducibility and excellent colour fastness their consumption is high. These issues affect the coloration of protein/cellulosic blends and attempts are extended to overcome such challenges. The fabric is repeatedly washed (after dyeing) with aqueous surfactants to remove excess/unfixed dyestuff. These shortcomings may be avoided by the use of 2.5 % o.m.f. of hexamethylenetetramine (hexamine), which decomposes at the boil to give ammonia and formaldehyde and this is actually a big problem due to the C&L of Formaldehyde, Mutagen 2 and Carcinogenic 1B. This treatment improves the penetration of after-treating agent, and results in a more effective removal of unfixed dye at a lower pH (6.5 as against 9.5)

3.2.3. Sulphur Black 001

Sulphur dyes have been traditionally used for dyeing cellulosic materials, in particular for dark navy and black shades on cotton. This study investigates the feasibility of using the dyestuff CI Sulphur Black 1 as a cost-effective, metal-free alternative to reactive and chrome dyes, to produce deep black shades on wool with high fastness levels. The new wool dyeing procedure uses sodium borohydride and sodium bisulphite as the reducing system for the sulphur dyes. Results are presented on the colour parameters, fastness to washing, alkaline perspiration, light, dry and wet rubbing, and wet burst strength of wool fabrics after dyeing with the sulphur dye. The results have been compared with those of wool dyed by conventional methods with a chrome black and a reactive black dye. It has been shown that the sulphur dye can be used



to produce a deep black shade on wool that is comparable with that obtained with either a reactive or chrome black dyestuff. With the exception of wet rubbing, the fastness properties are generally similar, or better than, those of the reactive and chrome dyes, but fibre damage is greater. Some further work is therefore required to overcome these two disadvantages. (Cai, 2012).

3.2.4. Others

In the company several attempts in using Cr(III) salts have been performed, with several salts. No literature was reporting the possibility to have the same effect and also experiments within the company didn’t lead to any significant result.



3.2.5. Data searches

Data sources are listed below: Following databases were searched to recover information on chemicals or guidance in composing the present document: CCRIS (Chemical Carcinogenesis Information); http://toxnet/nlm.nih.gov ChemIDplus (Chemical Identification/Dictionary); http://toxnet/nlm.nih.gov CHRIS (Chemical Hazards Response Information System); http://www.nisc.com/cis/qcis1.asp CPDB (Carcinogenic Potency Database); http://toxnet/nlm.nih.gov DART (Developmental Toxicology Literature) http://toxnet/nlm.nih.gov European Chemical Agency http://echa.europa.eu/web/guest European Environment Agency http://www.eea.europa.eu/themes/chemicals GENETOX (Genetic Toxicology Data); http://toxnet/nlm.nih.gov Haz-Map (Occupational Exposure/Toxicology); http://www.haz-map.com/refernc.htm. HSDB (Hazardous Substances Data Bank); http://toxnet/nlm.nih.gov IRIS (Integrated Risk Information System); http://toxnet/nlm.nih.gov NTP (National Toxicological Program) http://ntp.niehs.nih.gov/ RTECS (Registry of Toxic Effects of Chemical Substances); http://toxnet/nlm.nih.gov TSCA (Toxic Substances Control Act). http://www.epa.gov/oppt/existingchemicals/pubs/tscainventory/ United States Environmental Protection Agency http://www.epa.gov/

3.2.6. Consultations

To complete this document and collect all information about the Analysis of Alternatives several companies and company-functions have been involved: The involved functions within the company have been mainly the R&D and the Production Plant Responsible, the Commercial/Sales Responsible and the Manager Director.

4. SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES

Despite the apparent capability of reactive dyes to completely substitute the Mordant/Chrome system dyes, this is not possible for some special wools like

Lamb wool (Carbonized)

Sheep wool (Carbonised)

Alpaca wool

Mohair

Dead wool With the above wool it is not possible to reach a sufficient homogeneity in the colour as demonstrated in the following dyeing experiments:

http://toxnet.nlm.nih.gov/





http://www.haz-map.com/refernc.htm






Blue Dyeing on lamb wool



Brown Dyeing on sheep wool



Black Dyeing on Alpaca

Furthermore it has to be considered that in some cases the colour can reach the right homogeneity, but it will fail in obtaining the same brightness and sensation of colour fullness like with chrome dyes. The following pictures cannot obviously demonstrate clearly what it is meant actually, but for a similar formulation, where the Reactive Dye create a clear homogeneity of dyeing, the following samples have been generated to evaluate the other colour characteristics and they have clearly not passed the requests of the customer in terms of brightness This effect can be only perceived exposing the sample to a specific diagonal light (each customer often imposes his own specific light) and results in big differences when the fiber is spinned and then wowen.



Apart from qualitative visual evaluation, the measurements with the spectrophotometer have been performed in order to quantify the difference. A yield lower than about 8 % is evident when using a TL84 lamp

Reactive

Mordant



4.1. Substance ID and properties

In the following the summary of the two different set of formulations for wool dyeing, with the specific characteristics of the used dyes:

Reactive Dyes

REACH Not Registered Registered Not Registered Registered Registered Registered

C&L Existing data indicate a concern for H334; H317

H334; H317 Not classified H317 Not classified H334; H317

Functional family

Mordant Dyes

REACH Not Registered Registered Not Registered Not Registered Not Registered

C&L Notifications indicate a concern for the environment

Not classified Notifications indicate a concern for the environment

Notifications indicate no concern

Existing data indicate a concern for the environment

Functional Family



4.2. Reduction of overall risk due to transition to the alternative

As can be noticed from the table above, the Reactive Dyes are classified for Skin and also often for Respiratory sensitisation. This classification is not always supported by experimental data on animals. In fact, for example, according to EU Guidelines, Reactive Black 5 was not sensitizing in the guinea pig maximization test. However, literature data report on urticaria and eczema observed in workers with a high occupational exposure to reactive dyes. Consequently, it was agreed between members of the ETAD to classify Reactive Black 5 as skin sensitizer as well as all similar Reactive Dyes. Similarly, according to EU Guidelines, Reactive Black 5 was not sensitizing in an inhalative guinea pig sensitization test performed according to the European Discussion Group of Inhalation Toxicologists (EDIT) (referring to Botham P.A., Rattraya N.J., Woodcocka D.R., Walsha S.T. and Hexta P.M. "The induction of respiratory allergy in guinea-pigs following intradermal injection of trimellitic anhydride: a comparison with the response to 2,4-dinitrochlorobenzene ", Toxicology Letters, Volume 47, Issue 1, April 1989, Pages 25-39). However, literature data report on symptoms of respiratory allergy observed in workers with a high occupational exposure to reactive dyes. Consequently, it was agreed between members of the ETAD to classify Reactive Black 5 as respiratory sensitizer, as well as all similar Reactive Dyes. Sensitisation is a “non-threshold endpoint”, often considered of equivalent concern than CMR properties. On the other side, the Mordant dyes themselves have no sensitisation or other human health concern; they occasionally present some environmental concern, but those concern are managed already, since the release conditions are strictly controlled due to the Sodium dichromate and the other constituents the dyeing formulation

On the other side, it has to be considered what described above, in section 3.2.1, where it has been reported that based on the quality control implemented withinin the company it has been verified that Reactive marketed products are very often not free of impurities like p-chloro anlyline and 2-naphtylamine, two amines listed between the EU banned aromatic amines for their CMR properties.

Finally, as described in section 3.2.2, poor dye fixation has been a longstanding problem with reactive dyes and the fabric is repeatedly washed (after dyeing) with aqueous surfactants to remove excess/unfixed dyestuff. These shortcomings are avoided by the use of 2.5% o.m.f. of hexamethylenetetramine, which decomposes during boiling to give ammonia and formaldehyde and this is actually a big problem due to the fact that formaldehyde is classified as Mutagen 2 and Carcinogenic 1B. As a conclusion, it is not completely demonstrated that from a human health point of view, the use of Reactive Dyes is a safer solution than the use of Mordant Dyes

4.3. Economic feasibility

The Economic feasibility has been evaluated on the following elements, detailed in the Socio Economic Analysis (Section 4.5):

Raw material cost

Process costs

Customer validation

R&D work for formulation adaptation



4.3.1. Cost of Raw Materials per formulation

An overview of the raw material cost per formulation has been taken into account, considering the whole formulation (also additives needing to obtain the same effect) and the results are the followings:

Blue with Reactive dyes Brown with Reactive dyes Black with Reactive dyes

Blue with Mordant dyes Brown with Mordant dyes Black with Mordant dyes

Those costs have been calculated on real formulations actually implemented within the company. It can be noticed that the formulation costs are sensibly increased with the use of Reactive Dyes, from 0.1 to 0.,9 €, resulting in a medium value of 0.5 € per kg of dyed fiber

4.3.2. Process costs

The process is described in details in the following diagrams, which monitor the following parameters:

Time (represented in the ordinate (x)-axis)

Temperature (represented in the abscissa (y) axis)

Water consumption (in conjunction with the violet axis a washing cycle is recorded, which imply theuse of 60 liters of water)

Process with Reactive dyes



For the process with the reactive dyes:

Time: the overall time from the beginning to the discharge is about

Temperature: three temperature ramps are recorded:

Water consumption: three/four washing cycle are recorded with the use of a total of

Process with Mordant dyes

For the process with the mordant dyes:

Time: the overall time from the beginning to the discharge is about

Temperature: two temperature ramps are recorded:

Water consumption: one washing cycle with the use of

In this respect, from an efficiency, energetical and environmental point of view, the process with Chrome is much more competitive respect to the process with Reactive dyes:

Mordant dyes/chrome process Reactive dyes process

Time



Temperature

Energy

Water

*Assuming 6000 Kg of water per batch *Assuming the specific water calor = 4.184 kJ/kg °C

The process with Mordant Dyes presents a sensitive reduction in Time, Energy and Water consumption. Two hours of working time means a 25 % of reduction over the working day; from the point of view of a small and versatile company like Gruppo Colle it can be the competitive key that let the company answer to the requests of a market like fashion, which is always changing and developing along the periods of the year. Water and energy consumption don’t have to be underestimated, again respect to the big environmental issue, that is actually of outmost importance, since the Risk for human health are completely controlled by operative procedures. The related economical impact will be described in detail in the Socio Economic Analysis (Section 4.5)

4.3.3. Research & implementation of the Reacive Dyes process

In the non-use scenario, the substitution of chrome with Reactive Dyes can be made obtaining the same effect at higher costs in of the existing formulations in Gruppo Colle. This work has not started yet because of the economical burden and tight market request if not in some occasional experiments like the ones described above. Therefore it has also to be verified that for all those formulations the substitution and the conditions of obtaining the same effect can be found. The estimation of the time actually needing in R&D to adapt most of formulations with the use of Reactive dyes is based on the number of formulations that have been produced at least once in the last three years; it means that the conditions have to be adapted and optimised for . The following estimation can be made:

Number of formulations

time for adaptation (medium in hours)

Total hours

Working days (8 hours/day-2 resources)

Years (225 working days/year) 5.42

With the assumption of having two resources working at the re-formulation/substitution full time, about 5/6 years are needing to adapt, if possible, all existing recipes actually in use at Gruppo Colle.

4.3.4. Plant modification investment

No main process modification in the production of the devices is expected



4.3.5. Availability

Reactive Dyes are available on the market in sufficient quantity for this production and with an affordable price.

4.3.6. Customers approval

Development and implementation of the new formulations with Reactive Dyes has still to be finalised and accepted by customers. Customers of Gruppo Colle are the highest name of Fashion like:

The approval process of the new formulations follows several steps and can last up to one year for formulation, losing in the meantime the possibility to sell to the specific customer, not only the dyed wool, but also the whole product package.

5. OVERALL CONCLUSIONS ON SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES FOR USE

In the following table the comparison between PROs and CONs of the alternatives is presented, according to the following aspects:

Human Health aspects

Environmental aspects

Economical aspects

Technical feasibility



Overall comparing of alternatives

Reactive Dyes Mordant Dyes

PROS CONS PROS CONS

Health aspects

Not classified as carcinogen (category 1B), mutagen (category 1B) and toxic for reproduction (category 1B) in themselves

Use of Chrome, classified as carcinogen (category 1B), mutagen (category 1B) and toxic for reproduction (category 1B)

Classification as skin and respiratory sensitizers

Dyes in themselves have no concerns for human health at all

There is no demonstration that the treated articled do not maintain the sensitisation potential

Treated articles are regularly checked for chrome residuals

Contain EU banned aromatic amines

Do not contain EU banned aromatic amines

Use of fixation agents that release formaldehyde, classified as Mutagen 2 and Carcinogenic 1B

Do not use further fixation agents with formaldehyde release

Environmental aspects

Dyes in themselves have no concern for the environment

Dyes in themselves have some concern for the environment, but the RMM measures applied for Chrome and the whole process are enough to pose no risk for the environment

Water consumption is at least twice than for mordant dyes

Low water consumption

Low or not complete fixation lead to higher water quantity to be treated in the STP or in dedicated external facilities

High fixation rate

The process requires higher energy consumption

Low thermal energy consumption



Overall comparing of alternatives

Reactive Dyes Mordant Dyes

PROS CONS PROS CONS

Economical aspects

Higher costs for raw materials Low raw material costs

Higher costs for water consumption

Low water consumption

Higher costs for energy consumption

Low energy consumption

Higher costs for process time consumption

Low process time consumption

High costs for R&D for formulation adaptations

No R&D costs

Feasibility

Not for all applications the substitution is possible (for specific wools no acceptable dyeing properties are obtained)

High performances on all substrates

Substitution (where feasible) will take money and time

Long time for substitution



As an overall conclusion it can be stated that regarding the existing alternatives the following results have been obtained: Technical performance: only partially achieved Human health aspects: only partially achieved Environmental aspects: not achieved Economical aspects not achieved

5.1. Technical performance

It has been verified that in some cases, for some specific wool, there is no possibility to obtain the same dyeing performance with any different dye or technology. Potentially, also considering the difference in costs and timing, only 65 % of the existing formulations in Gruppo Colle can be technically substituted with Reactive dyes. This work has not started yet because of the economical burden and tight market request if not in some occasional experiments like the ones described in the Analysis of Alternative document. Therefore it has also to be verified that for all those formulations the substitution and the conditions of obtaining the same effect must still be found. The estimation of the time actually needing in R&D to adapt most of formulations with the use of Reactive dyes is based on the number of formulations that have been produced at least once in the last three years; it means that the conditions have to be adapted and optimized for The following estimation can be made:

Number of formulations

time for adaptation (medium in hours)

Total hours

Working days (8 hours/day)

Years (225 working days/year) 5.42

With the assumption of having one resource working at the re-formulation/substitution full time, about 5/6 years are needing to adapt, if possible, all existing recipes actually in use at Gruppo Colle. The technical problem of the remaining 35 % that it is not possible to substitute with Reactive dyes has still not found any potential solution and a R&D project has to be studied, budgeted and organized.

5.2. Human health aspects

Reactive Dyes are classified for Skin and also often for Respiratory sensitisation. Sensitisation is a “non-threshold endpoint”, often considered of equivalent concern than CMR properties. On the other side, the Mordant dyes themselves have no sensitisation or other human health concern; they occasionally present some environmental concern, but those concern are managed already, since the release conditions are strictly controlled due to the Sodium dichromate and the other constituents the dyeing formulation

On the other side, based on the quality control implemented within the company it has been verified that Reactive marketed products are very often not free of impurities like p-chloro anlyline and 2-naphtylamine, two amines listed between the EU banned aromatic amines for their CMR properties.



Finally, poor dye fixation has been a longstanding problem with reactive dyes and the fabric is repeatedly washed (after dyeing) with aqueous surfactants to remove excess/unfixed dyestuff. These shortcomings are avoided by the use of 2.5 % o.m.f. of hexamethylenetetramine, which decomposes at the boil to give ammonia and formaldehyde and this is actually a big problem due to the fact that formaldehyde is classified as Mutagen 2 and Carcinogenic 1B. As a conclusion, it is not completely demonstrated that from a human health point of view, the use of Reactive Dyes is a safer solution than the use of Mordant Dyes and to really improve the human health aspects completely new formulations with safer dyes have to be studied and optimized.

5.3. Environmental aspects

As described in the Analysis of Alternatives, section 4.3.2, from an efficiency, energetically and environmental point of view, the process with Chrome is much more competitive respect to the process with Reactive dyes. Based on the actual knowledge, there is no existing process that can improve those conditions in order to get the same dyeing properties. This has an impact on the overall costs of the substitution.

5.4. Economical aspects

The higher raw material cost for Reactive Dyes formulation together with the process costs described in the Analysis of Alternatives, section 4.3.2 sensibly increases the overall costs for substitution. This analysis is also described more in deep in the Socio economical Analysis. As a consequence for the time being no valid alternative is available but a substitution project needs to be started.

5.5. List of actions

It is demonstrated that no valid alternative is available up to now, nevertheless a number of activities will be put forwards in order to adapt the existing potential alternatives to the use of Chromate salts to the requests of Gruppo Colle. Tier 1 Implement the substitution of the main formulation with Reactive Dyes where the technical performance can be reached This activity can take from 4 to 6 years Tier 2 Start an R&D project in order to achieve the same effect also in those cases where it impossible today This activity can take from 2 to 5 years Tier 3 Start an R&D project to optimise the process conditions and obtain the same results focusing on the Environmental aspects like Water consumption, Energy consumption and Timing This activity can take from 3 to 5 years



Tier 4 Evaluating potential new alternatives In total a substitution plan will last from a minimum of 6 to10 years.



ANNEX I – REFERENCES

Ashis, K. S. (2011). Dyeing of Textiles with Natural Dyes. Cai, R. M. (2012). Volume 128, Issue 1. Lewis, D. (1992). Wool dyeing. West Yorkshire: Society of Dyers and Colourists. Sawatwarakul, W. (2014). A Diagnostic Expert System for the Dyeing of Protein Fibers - A dissertation submitted to the Graduate Faculty of North Carolina State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Fiber and Polymer Science. Raleigh, North Carolina. SUBSPORT. (2015). Kooperationstelle Hamburg IFE GmbH;. Hamburg: (Substitution Support Portal).



ANNEX II – JUSTIFICATIONS FOR CONFIDENTIALITY CLAIMS

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ANALYSIS OF ALTERNATIVES - ECHA

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