Submission Of Information On - Europa
Submission of information onTEMPLATEfor third party submission of information on alternatives forApplications for AuthorisationNON-CONFIDENTIALLegal name of submitter(s):Heubach GmbH, Germany[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)TABLE OF CONTENTS1. ALTERNATIVE ID AND PROPERTIES. 32. TECHNICAL FEASIBILITY . 53. ECONOMIC FEASIBILITY. 124. HAZARDS AND RISKS OF THE ALTERNATIVE . 135. AVAILABILITY . 136. CONCLUSION ON SUITABILITY AND AVAILABILITY OF THE ALTERNATIVE . 137. OTHER COMMENTS. 13REFERENCES . 13APPENDIXES.14[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]2
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)1. ALTERNATIVE ID AND PROPERTIESThere is not a single alternative pigment existing to exactly replace a specific PY 34 or PR 104pigment. The solution to reformulate lead-containing paints is the smart combination ofsuitable organic and inorganic pigments.The formulation of colours using pigment combinations is state of the art. For this reasonpigment combinations, hybrid pigments and pigment preparations have already been in use toreplace lead pigments for a long time. This can be seen from the worldwide figures inconsumption of PR 104 and PY 34:Overview on global consumption of PY34 and PR 104:2000: 90.000 t (Source: European Coatings; Vincentz Verlag)2006: 68.000 t (Source: Strategic Research Insights)2010: approx. 40.000 t (Estimation by Heubach)Tico for plasticsThese are countertypes, developed to match the colour space that is usually covered bythe traditional Chrome Yellow and Molybdate Red pigments.These Titanium based colorants exhibit maximum gloss, opacity strength and durability.It is made by a proprietary co-finishing process to attach the organic colorants to thesurface of the titanium carrier pigments.This Hybrid-Pigment series can also be used to generate all of the RAL colour tones thatare usually made with Chrome Yellow and Molybdate Red pigments.Ecopaque for Plastics Series 13Ecopaque pigments of the 13-series are special preparations based upon the hightemperature resistant range of Heucodur Pigments combined with high performanceorganic pigments. Ecopaque pigments are alternatives to traditional Chrome Yellow andMolybdate Red pigments.They are recommended for use in PE, PVC PP, PS and ABS systems.The 7 grades represent the colour space of Lemon Chrome via Middle chrome to scarletpigments.HEUCOFIT LRThis series is developed as direct alternative to the traditional Chrome Yellow andMolybdate Red Heucotron gradesHeucotron Yellow 1064Middle ChromeHeucotron Yellow 1070Red Shade chromeHeucotron Red 220Scarlet.[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]3
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)The three counter grades are preparations of heat stable inorganic pigments based onNickel and Chrome Rutile pigments to achieve opacity and utilizing the brilliance andcolour strength of relevant organic pigments.The 3 preparations are showing a similar opacity and are very close in respect to colourstrength and brilliance.The light and weather stability of these preparations are in line or better than thetraditional Chrome Yellow and Molybdate Red pigments. The yellow preparations aresuitable for temperatures up to 190 C and the red version is suitable to 230 C. Withthis heat stability most of the PVC and PO applications can be met.[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]4
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)2. TECHNICAL FEASIBILITYTico for plasticsThese Hybrid pigments are made by a proprietary co-finishing process to attach theorganic colorants on the surface of titanium yellow carrier pigments. The colour matchis demonstrated in the plaques in Polystyrene below:Tico Yellow 599 KChrome Yellow1:10 reductionTico Red 643 KMolybdate Red1:10 reductionFig 1: Colour comparison Tico Yellow and Red vs. Chrome Yellow and Molybdate Red[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]5
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)The tinting strength advantage that allows reduced pigmentation is demonstrated in thefollowing diagram:Tico Yellow 599 KStd. 100%Medium chromeyellowP.Y. 34 lead chrome (HT5)P.Y. 34 lead chrome (HT8070)Std. 100%Tico Yellow 593 KP.Y. 34 lead chrome (HT13)Lemon chromeyellowP.Y. 34 lead chrome (HT8064)0%25%50%75%100%125%150%Graph 1: Tinting strength comparison Tico Yellow vs. lead chromatesThe superior heat stability in HDPE of the Hybrid Pigments is demonstrated in thefollowing graphs:Tico Yellow 599 KColor difference acc. to DIN 53772201612Heat stability HD-PE 280 C84Heucotron T 80700200Heat stability HD-PE 240 C220240260280Temperature [ C]300320Sample: 5 min at given temperatureStandard: 0 min 200 CGraph 2: Heat stability of Tico Yellow vs. Chrome Yellow[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]6
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)And the light and weather fastness is matching or superior to the traditional ChromeYellow and Molybdate Red pigments as demonstrated in the graph below.Accelerated weathering in PMMA Acrylic resinafter 2000h in Xenon4Delta E3210Tico Yellow 599Chrome YellowGraph 3: Xenon test results of Tico Yellow vs. Standard Chrome YellowTinting strengthThe same principles are valid for the replacement of the scarlet pigment.Also here the tinting strength advantage allows reduced pigmentation and isdemonstrated in the following diagram:Std. 100%Tico Red 643 Kmolybdate red 1molybdate red 2Std. 100%Hiding powerTico Red 643molybdate red 1molybdate red 20%25%50%75%100%125%150%Graph 4: Tinting strength and hiding power comparison of Tico Red vs. Molybate Reds[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]7
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)The superior heat stability in HD PE of the Hybrid Pigments compared to a typical hightemperature Molybdate pigment is demonstrated in the following graphs:Tico Red 643 KColor difference acc. to DIN 537722016128Heat stability HD-PE 300 C40Heucotron T 8025200220240260280300320Temperature [ C]Heat stability HD-PE 260 CSample: 5 min at given temperatureStandard: 0 min 200 CGraph 5: Heat stability of Tico Red vs. Molybdate RedAnd the light and weather fastness is matching or superior to the traditional ChromeYellow and Molybdate Red pigments as demonstrated in the graph below.Accelerated weathering in PMMA Acrylic resinafter 2000h in Xenon54Delta E3210Tico Red 643 KMolybdate RedGraph 6: Xenon test results of Tico Red vs. Molybdate RedEcopaque for PlasticsThis is a set of special preparations based upon the high temperature resistant range ofHeucodur Pigments combined with high performance organic pigments.The temperature stability is 250 C for the Ecopaque preparations and the lightstability offers similar to better performance compared with the traditional ChromeYellow and Molybdate Red pigments and are judged to be in the range of 6-7.The colour comparison as shown below demonstrates the colour space that can becovered with these special pigment preparations:[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]8
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)Ecopaque - PigmentsFig. 2: Colour space of EcopaqueTechnical 5,02021231624304-54-54-54-54-54-5T emperatureresistanc e Conto migratiesssFastnr g/ 100Nu mbeD OPy l/ kden sitBulkDensity , g/mlggEcopaque - Pigments 250 250 250 250 250 250Tab. 1: Technical data of Ecopaque PreparationsHEUCOFIT LRHeucofit LR Yellow vs. Chrome YellowsThis series is developed as direct alternative to the major lead chromate pigments incoatings applications, but can also be used in low temperature plastics application likePVC.The following colour comparison indicates the colour match in Chroma and Hue of theyellow alternatives.[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]9
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)Colour match in LLDPEStandard Lemon ChromeStandard Middle ChromeHeucofit LR1006401Heucotron1064Heucofit LR1007001ΔE 1:5 reduction1,5Heucotron1070ΔE 1:5 reduction0,7Fig. 3: Colour comparison of Heucofit LR Yellows vs. Chrome YellowsEven though the numerical DE values in full tone shows some variation, the realcomparison in the colour shows a close match.The heat stability in plastics of 200 C in HDPE, with no significant colour change,allows the use in LLDPE and PVC applications. The following picture illustrates the heatstability is similar to the traditional Chrome Yellow. The heat stability limit of 200 C isrelated to the stability of one component of the preparation.Heucofit LR Yellow 1007001Standard 180 CHDPE 2% Pigment5Min 180 5 Min 200 C5 Min 220 C5Min 180 5 Min 200 C5 Min 220 CHeucotron Yellow 1070Standard 180 CFig. 4: Heat stability of Heucofit LR Yellow vs. Chrome YellowThe light fastness of 7 according to EN ISO 105 B01 and the weathering resultsperformed in coating systems according EN ISO 20105-A02 also show the sameperformance as a traditional Chrome Yellow pigments.[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]10
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)Heucofit LR vs. Molybdate RedSimilar to the Chrome Yellows an alternative preparation for the scarlet version wasdeveloped. The following draw down indicates a very close match in Chroma, Hue andOpacity for the scarlet alternative of traditional Molybdate Red pigmentsStandard ScarletHeucofit LR3022001Heucotron220Fig. 5: Colour comparison of Heucofit LR Red vs. Molybdate RedEven though the numerical DE values in full tone show some variation, the realcomparison in the colour shows a close match. The products can be used to achieve thecolour space that is usually met by the traditional Chrome Yellow and Molybdate Redpigments.The light fastness of 7 according to EN ISO 105 B01 and the weathering resultsperformed in coating systems according EN ISO 20105-A02 also show the sameperformance as a traditional Molybdate Red pigment.The heat stability in plastics of 240 C is the same as a standard Molybdate red, asillustrated below and allows the use in most Polyolefin and PVC applications.[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]11
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)Heucofit LR Red 3022001Standard 180 C5Min 180 5 Min 200 C5 Min 220 C5 Min 240 C5 Min 260 C5Min 180 5 Min 200 C5 Min 220 C5 Min 240 C5 Min 260 CHeucotron Red 220Standard 180 CFig. 6: Heat stability of Heucofit LR Red vs Molybdate RedEcopaque for PlasticsThis is a set of special preparations based upon the high temperature resistant range ofHeucodur Pigments blended with high performance organic pigments.The temperature stability is 280 C for all the Ecopaque preparations and the lightstability offers similar to better performance compared with the traditional ChromeYellow and Molybdate Red pigments and are judged to be in the range of 6-7.The colour comparison as shown below demonstrates the colour space that can becovered with these special pigment preparations:3. ECONOMIC FEASIBILITYAs demonstrated above the Hybrid pigments and the selected pigment preparationsoffer an increased tinting strength, a superior brilliance and better hiding power.Therefore it is not realistic to compare the prices of the pigments directly. Tounderstand the economic impact it is necessary to compare the final formulation. Incertain RAL colours it could be shown that the cost for the pigments is in the range of1,5 – 2,5 times the cost of using traditional Chrome Yellow and Molybdate Redpigments.At the same time, due to the low amount of pigments (in the range of 0.1% to 5%)being used to achieve a final colour, the impact of the cost of pigments in the finalproducts like a truck tarpaulin, a plastic chair is or a window frame is only minor. Evenwith higher prices for the pigments it is unlikely that this will lead to a higher price forthe finished goods.[0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]12
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)4. HAZARDS AND RISKS OF THE ALTERNATIVEAll alternative pigments and pigment preparations described above are not classified ascarcinogenic, mutagenic or reprotoxic (CMR) substance or mixture according to the criteriagiven by REGULATION (EC) No 1272/2008 OF THE EUROPEAN PARLIAMENT AND OF THECOUNCIL of 16 December 2008 on classification, labelling and packaging of substances andmixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amendingRegulation (EC) No 1907/2006 (CLP regulation).The majority of the alternative pigments or pigment preparations are not classified ashazardous according to CLP regulation. Therefore we consider the alternatives to besignificantly less hazardous than the lead chromate based pigments.Details of the classification of the described alternative pigments are given in the table inAppendix I.5. AVAILABILITYAll the above mentioned pigment preparations based on pigments which are industrialproducts that are produced already for a long period at several pigment producersaround the world. Current capacity for most of these pigments is higher than demand.And producers like Heubach have debottlenecking projects ready in case the demand ispicking up more than expected.As demonstrated over the last 10 years when the demand of for the traditional ChromeYellow and Molybdate Red pigments has decreased from 90.000 tpy to roughly onethird today, the pigment producers could easily cope with the demand for substitutepigments.6. CONCLUSION ON SUITABILITY AND AVAILABILITY OF THE ALTERNATIVEThe replacement of lead chromates and molybdate reds in plastics and otherthermoplastic materials is technically possible by several pigment preparations. Highercosts for these pigment preparations must however often be accepted, but very oftenthe price increase of the pigments preparations is a negligible percentage of theproduction cost of the whole article. Availability of these standard pigments that areused in these combinations is given or can be made available through debottleneckingprojects.7. OTHER COMMENTS[Insert text here]REFERENCES[Insert text here][0012-07 – 0012-10] [pigment mixtures] [April 8th, 2014]13
APPENDIXESAppendix I: Classification of the alternative pigments and pigment ionReferenceforclassificationRemarksSupplierCarc. 1B; H350Repr. 1A; H360 DfSTOT RE 2; H373**Aquatic Acute 1; H400Aquatic Chronic 1;H410Carc. 1B; H350Repr. 1A; H360 DfSTOT RE 2; H373**Aquatic Acute 1; H400Aquatic Chronic 1;H410CLP RegulationAnnex VIHeubach GmbHCLP RegulationAnnex VIHeubach GmbHMixtureno classificationHeubach GmbHMixtureno classificationMixtureno classificationMixtureno classificationMixtureno classificationMixtureno classificationMixtureno classificationSupplier safetydata sheetSupplier safetydata sheetSupplier safetydata sheetSupplier safetydata sheetSupplier safetydata sheetSupplier safetydata sheetSupplier safetydata sheetLead chromate based 25PY34lead sulfochromateyellowEC-No. 215-693-7PR104lead chromate molybdatesulfate redEC-No. 235-759-9Alternative pigment preparationsECOPAQUEYellow 13 102ECOPAQUEYellow 13 103ECOPAQUEYellow 13 106ECOPAQUEOrange 13 222ECOPAQUEOrange 13 250ECOPAQUE Red13 327Heucofit LRRed 3022001[0012-07 – 0012-10] [pigment mixtures] [April 7th, 2014]14Heubach GmbHHeubach GmbHHeubach GmbHHeubach GmbHHeubach GmbHHeubach GmbH
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)ProductColourIndexHeucofit classificationRemarksSupplierMixtureno classificationSupplierinformationHeubach GmbHHeucofit LRYellow1007001Mixtureno classificationSupplier safetydata sheetMixture contains an diarylide pigment. Ingeneral diarylide pigments are notrecommended for application above 200 C, due to decomposition of the pigmentwhich might lead to the formation ofaromatic amines. However it is asuitable alternative for low temperatureapplications.Mixture contains an diarylide pigment. Ingeneral diarylide pigments are notrecommended for application above 200 C, due to decomposition of the pigmentwhich might lead to the formation ofaromatic amines. However it is asuitable alternative for low temperatureapplications.TICO Yellow599KTICO Yellow593KTICO Red 643KMixtureno classificationMixtureno classificationMixtureno classificationSupplier safetydata sheetSupplier safetydata sheetSupplier safetydata sheet[0012-07 – 0012-10] [pigment mixtures] [April 7th, 2014]15Heubach GmbHHeubach GmbHHeubach GmbHHeubach GmbH
2000: 90.000 t (Source: European Coatings; Vincentz Verlag) 2006: 68.000 t (Source: Strategic Research Insights) 2010: approx. 40.000 t (Estimation by Heubach) Tico for plastics These are countertypes, developed to match the colour space that is usually covered by
002 europa league fc rostov maccabi haifa 1 - 2 v 2-3 - - - si 003 europa league djurgarden cfr 1907 cluj 0 - 1 v 0-1 - - - no 004 europa league ns mura psv 1 - 5 v 4 o - - - si 005 europa league rosenborg alanyaspor 1 - 0 l 0-1 - - - no 006 europa league willem ii rangers 0 - 4 v 4 o - - - no 010 europa league besiktas rio ave 1 - 1 e 2-3 .
CTD2 Dashboard Submission Builder Tutorial 5 Figure 4: Provide the requested information for the submitter and submission. Guidelines to fill in the fields under the Submission Description Submission Name: A Submission is a Dashboard entry that represents a dataset associated with positive experimental results, a set of data-related figures, or a story.
UEFA Europa League –21:00– CFR 1907 Cluj v Roma (Live on ) UEFA Europa League –18:55– Maccabi Tel-Aviv v Villarreal (Live on ) UEFA Europa League –21:00– AZ Alkmaar v Real Sociedad (Live on ) UEFA Europa League –18:55– Slovan liberec v Hoffenheim (Live on )
S.01.01 - Content of submission Background 7. Template S.01.01 is a core template, both at annual and quarterly reporting, and describes the content of each submission sent to NSAs. It allows supervisors to assess completeness and coherence of the submission. 8. No major issues reported but when using it for the purposes for example of
ACC.21 Abstract Submission Instructions Logging onto the ACC Submission System You can begin your abstract submission by visiting the “Submit Your Science” tab on the ACC.21 site. Entering Abstract Information A. Title 1. Abstract titles will be in all CAPS. The system will automatically convert all letters to caps after you
Figure 9: E-File Document Page - Manual Submission Section B. The ACCESS Document Information Page for a manual submission appears (See Figure 8, above). Each document volume or logical grouping of a manual submission must not exceed 500 pages. The cover sheet can be used for a 500 page document or for the first volume of a submission that exceeds
SAMPLE . SUBMISSION FORM. THINGS TO CONSIDER AS YOU BEGIN YOUR SUBMISSION: An * indicates that a value is required before submitting this form. Unless otherwise noted, questions apply to all session formats. You may start a submission and complete it at a later time. The information on each page will not be saved
Historia de España Tema 04: Los Borbones y la crisis del Antiguo Régimen Curso 2020/21 1 de 29 Europa en el siglo XVIII ESPAÑA EUROPA GRAN BRETAÑA población abundante en interior que en periferia (s.e. en el s. XVIII crece más en la periferia, dinámica que llega hasta hoy en día) 01
