The future of organic colorants in Czech Republic, influence of EU legislation, end-users requirements and standards Ing. Jana Minaříková Ing. Martin Němec mnemec@synthesia.eu XXIV. IFATCC 15.06.2016 Pardubice
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Synthesia, a.s. Is the major European producer of qualified chemistry With 1625 employees, turnover 125 million EUR and almost 95 years long tradition produce hundreds of product for customers in 60 countries all over the world Consists of: - SBU Pigments and Dyes – production of organic pigments and dyes - SBU Nitrocellulose - SBU Organic Chemistry - SBU Energetics Is the one of the last producer of organic dyes in Europe
Dyestuffs application groups and changes through the decades.
Dyestuffs application groups and changes through the decades. The sale proportion of dyes and pigments The reasons of the changes: Production Turnover Dyes - Import of the cheap textile goods and dyes from Asia 1 400 t 13 mil. EUR Pigments - Pigments = more qualified chemistry 3 100 t 44 mil. EUR
The topics which have influence on the production of organic dyes REACH regulation, influences on productions of colorants, SVHC substances CLP issues, substances mixtures formation, properties combinations eventuating classification ETAD – code and principles, cooperation in chains to users and retailer ZDHC and MRSL issues Latest development in global sales and producers network in-groups (Inditex, OekoTex, GOTS etc.)
REACH regulation, influences on productions of colorants, SVHC substances. R egistration, E valuation, A uthorisation and Restriction of Ch emicals is a European Union regulation dated 18 December 2006. The purpose of this regulation is to protect human health and the environment. REACH requires manufacturers and importers of chemical substances (quantities of one tone or more per year per company) to register the substances in the European Chemicals Agency (ECHA). The registrations are accomplished in phases depending on tonnage and have a great impact on the textile and leather industry. The first registration deadline was in December 2010 when all the substances above 1,000 tones in addition to all the carcinogenic, mutagenic or toxic for reproduction substances (= 1 tone/year) and substances classified as dangerous for the aquatic environment (= 100 tonns/year)had to be registered. The last registration deadline is June 2018 for substances from 1 to 100 tones
REACH regulation, influences on productions of colorants, SVHC substances. REACH - costs • Raw materials (incl. Intermediates) • Substances – Toxicological tests – Documentation – Administrative works The most important parameter is number of registrants for the substance – many dyes have only 1 registrant. • 1 - 10 t/y min. 40 000 EUR • 10 - 100 t/y about 300 000 EUR Synthesia can provide for itself, but also for other interested companies, sufficient capacity for testing of chemicals due to 100% ownership of VUOS, a.s. – an accredited R & D institution. One department of VUOS, the Centre for Ecology, Toxicology and Analytics (CETA) approved for ecological, toxicological and analytical testing of chemical substances. This department performs practically all necessary experimental works and co-operates in other (expert, administrative etc.) works connected with the REACH regulation.
REACH regulation, influences on productions of colorants, SVHC substances. • SVHC = Substances of Very High Concern • A substance may be proposed as an SVHC if it meets one or more of the following criteria: – it is carcinogenic – it is mutagenic – it is toxic for reproduction (CMR) – it is persistent, bioaccumulative and toxic (PBT, vPvB) • Actually 168 substances, updating two times per year • Candidate List is the first step of the authorization procedure • Last changed on 17.12.2015, next expected on June 2016 • SVHC limit 0,1% = 1000 ppm in final goods Synthesia fulfills the limit SVHC at all colorants
REACH regulation, influences on productions of colorants, SVHC substances. Synthesia, a.s. has already registered 140 substances and raw materials according to REACH, mostly for the segment of organic pigments. "Now we are focusing on organic dyes - a priority for our company to 2018 “ • Currently about 800 substances - structures of dyes on the market • REACH registration about 400-500 substances in year 2018 • Synthesia will register about 60 substances (= 120 commercial colorants/dyes, costs 3.5 – 4.0 millions EUR)
REACH regulation, influences on productions of colorants, SVHC substances. Synthesia will register about 60 substances /structures of dyes (= 120 commercial colorants/dyes, powder and liquid forms, numbers of concentrations) Three basic groups of organic dyes
Reactive dyes (monochlortriazine) Direct dyes
Acid dyes (1:2 metal complex)
CLP issues, substances mixtures formation, properties combinations eventuating classification. C lassification, L abelling and P ackaging of substances and mixtures EU Regulation No. 1272/2008/EC CLP introduces into the EU the globally harmonised system for classifying and labelling chemicals. This means that the same system is now used throughout the world. Signal words R- and S- phrases H- and P- statements New pictograms
CLP issues, substances mixtures formation, properties combinations eventuating classification.
ETAD – code and principles, cooperation in chains to users and retailer E cological and T oxicological A ssociation of D yes and Organic Pigments Manufacturers • ETAD's mission for a sustainable growth in a colourful world • Industry cooperation to "minimize impact on health or environment“ • Representation and advocacy of members • Promotion of product stewardship • Harmonization of health and environmental regulations • Synthesia membership - more than 10 years • Active in Dyes OC, Pigments OC, Regulatory Affairs C. • Analytical methods, cooperation with authorities, EU commission for toys, food contact, EN/ ISO norms … • Code of Ethics – keeping of standards, limits, principles …
ZDHC and MRSL issues Z ero D ischarge of H azardous C hemicals ZDHC members Communication with ETAD, explaining technical possibilities to produce and limits of used methods The Zero Discharge of Hazardous Chemicals ZDHC group developed M anufacturing R estricted S ubstances L ist and published a MRSL www.roadmaptozero.com The MRSL restricts hazardous substances potentially used and discharged into the environment during manufacturing, not just those substances that could be present in finished products
ZDHC and MRSL issues ZDHC substances & limits
ZDHC and MRSL issues
ZDHC and MRSL issues
Latest development in global sales and producers network in-groups (Inditex, OekoTex, GOTS etc.) AZO dyes are the name of the group of synthetic dyestuffs based on nitrogen that are often used in textile industry. Some AZO dye stuffs may separate under certain conditions to produce carcinogenic and allergenic aromatic amines. The EU AZO Colorants Directive 2002/61/EC sets out that Azo dyes which may release one or more of the 22 aromatic amines (see next slide) in detectable concentrations, above 30 ppm in the finished articles or in the dyed components may not be used in textile and leather articles which may come into direct and prolonged contact with the human skin or oral cavity. The directive came into force in September 2003. Since Annex XVII of REACH came into force in 2009, the AZO Directive 2002/61/EC has been replaced by REACH regulation.
Latest development in global sales and producers network in-groups (Inditex, OekoTex, GOTS etc.) „Banned“ amines 4-Aminobiphenyl 3,3’ -Dimethylbenzidine Benzidine 4’ -Methylenedi-o-toluidine • DIRECTIVE 2002/61/EC 4-Chloro-o-toluidine p-Cresidine 2-Naphthylamine 4,4’ -Methylene-bis-(2-chloro-aniline) - AZO Colorants Directive (REACH Annex 17) o-Amino-azotoluene 4,4’ -Oxydianiline 22 amines 5-Nitro-o-toluidine 4,4’ -Thiodianiline • Inditex, OekoTex , ZDHC 4-Chloroaniline o-Toluidine - one of the world ´ s largest fashion groups 4-Methoxy-m- 4-Methyl-m-phenylenediamine - the international testing and certification phenylenediamine system for textiles 4,4’ -Methylenedianiline 2,4,5-Trimethylaniline 22 + 2 amines 3,3’ -Dichlorobenzidine 2-Methoxyaniline • GOTS 4.0 3,3’ -Dimethoxybenzidine 4-Amino-azobenzene – - the world ´ s leading processing standard aniline & N,N- – 2,4-xylidine & dimethylaniline & p- 2,6-xylidine for textiles made from organic fibres phenylendiamine 22 + 2 + 3 amines • Next step? The tendency regarding the integration of both The number of banned substances all legislation and end-users requirements will 22 + 2 + 3 + ?? amines increases and the limits decline be important priority in near future.
Important • The first step with starting new product (dye, colorant, aditive, final goods = complicated mixture/chemical coctail) is to evaluate compliance with legislation, asking certificate conditions etc. • Consult it with legislative dept. of your potencial customers and learn about application
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