### DISCLAIMER This report is the property ofClariant. Its content is confidential and not for general release. Itis not allowed to cite and reveal the report or its content to a third party without prior written approval of Clariant.

## REPORT Leuco SulfurBlack 1**9~515B** 

# harlanTM 

# ...

Determination ofthe Freezing Point 

## IFreezing Range

Data Requirements I 

### Test Guidelines:
Study Director: Test Facility:
Sponsor: EEC Directive 92/69, A.l OECDNo.102 Council Regulation (EC) No. 44012008, A. I

DrJens Franke 

### Harlan Laboratories Ltd. Zelgliweg 1 4452 Itingen 

### I Switzerland 

### Clariant Products (Switzerland) Ltd. Rothausstrasse 61 4132 Muttenz 1 

### I Switzerland 

### Study Identification: Harlan Laboratories Study 

### C30920 Version: Final 

### Study Completion Date: February 24, 2009 Page 1 of 16 

# ' CONTAINS NO CBI 

# I**fH~** 

# b /?l/\7-Harlan Laboratories Study C30920 Leuco Sulfur Black I 

## CONTENTS Report Page 2

CONTENTS ....................................................................................................................................2 LIST OF TABLES ..........................................................................................................................2 GLP CERTIFICATE.......................................................................................................................3 SIGNATURES ................................................................................................................................

### 4 STATEMENT OF COMPLIANCE ................................................................................................

### 5 QUALITY ASSURANCE GLP STATEMENT.............................................................................6 PREFACE .......................................................................................................................................7 General Information...............................................................................................................

### 7 Responsibilities......................................................................................................................7 Schedule.................................................................................................................................

### 7 DataRequirements 

### ITest Guidelines .................................................................................... 8 Archiving ............................................................................................................................... 8 Summary ofStudyPlan Amendments................................................................................... 

### 8 1 SUMMARY...........................................................................................................................9 2 PURPOSE............................................................................................................................ 10 3 MATERIALS AND METHODS......................................................................................... 11 3.1 Test Item ................................................................................................................ 11 3.2 Test System and Reagents ..................................................................................... 11 3.3 Principle oftheTest............................................................................................... 11 3.4 Performance ofthe Test......................................................................................... 12 3.4.1 Preliminary Test ...................................................................................... 12 3.4.2 Main Test................................................................................................. 12 3.5 DataHandling........................................................................................................ 13 4 RESULTS ............................................................................................................................ 14 

### 5 CONCLUSIONS ................................................................................................................. 15 6 TABLES .............................................................................................................................. 16 

## LIST OFTABLES Table 1 Determination ofthe Freezing Point ofLeuco Sulfur Black 1 (Summary) .................................................................................................................. 16

J' '.**.,_,.~..** ,... •Harlan Laboratories Study C30920 Leuco SulfurBlack 1 

## GLPCERTIFICATE Report

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### ~ ConftderuioM Svfner• Conftdtruiun svizra Fedtrel DepartmeM oftht iawltonment. 

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## Statement ofGLP Compliance According to Article 14 paragraph 3Ordinance on Good Laboratory Plac:llce (OGLP, SR 813.112.1) The notification euthority torchemlcals conftnns that the foDowing test facility was inspected with respectto the compnancewith the Swiss Ordinance on Good Laboratory Prectk:e, adopted on 18th May 2005 (OGLP, SR 813.112.1). This Ordinance Is based on the OECD Principles of Good Laboratory Practice, aa revised In 1997 and adopted on 26th November 1997 by decision of the OECD Councii(C(97)186/FinaQ. Unequivocal nama and address ofthetestfacility. Harlan Laboratories Ltd. lelgllweg 1 4452 ltingen, Switzerland. Areas ofexpertise according to article 3paragraph 1letterdOGLP: 1 JPhysical-chemical testing, 21Tox!cily studies, 4.1 Environmental toxicity studies on aquatic and terrestrial organisms, 51 Studies on behaviour In water, IOil and air; bioaccumulation, 81 Residue studies, 7 JStudies on eff8cts on mesocosms and natural ecosystems, 81 Analytical and clnlcal chemistrytasting, 9.1 Otherstudies (safety pharmacology and animal metabolism). Inspection authority: Federal Officeforthe Environment (FOEN) 1Federal Office of Public Heelth (FOPH) ISwiss Agencyfor Therapeutic Products (Swlssmedic) Date ofInspection: 05th to 09111 and 26th to 30th November2007 Date ofdec:laion: 30th April2008 Basad on the above mentioned dec:lslon It can be confirmed that the above mentioned test facitity Is able to conduct studies according to the aforementioned a1111s of expertise In compliance with the principles of GLP. The above mentioned te&t facility Is lstad In the •ter and GLP list according to the Article 14 OGLP and is Inspected on a regular basis according to Article 6 paragraph 2OGLP.

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• ..,.,._,fl41 1Dp1 12271015 f8C ..., fOJ!! IZIM• Page 3Harlan Laboratories Study C30920 Leuco SulfurBlack 1 

## SIGNATURES

StudyDirector:

Management: Report Page4



### DrJens Franke

::f!;( DrJom Schreitmiiller

Date: 

## "ll/oYUDn.f '2A l**~**Harlan Laboratories Study C30920 Leuco Sulfur Black 1 

### GOOD LABORATORY PRACTICE Report



## STATEMENT OF COMPLIANCE Harlan Laboratories Study: Test Item: StudyDirector: C30920 Leuco Sulfur Black 1 Dr Jens Franke Page 5

StudyTitle: Determination ofthe Freezing Point 

### I Freezing Range This studyhas been performed in compliance with the: Swiss Ordinance relating to Good Laboratory Practice adopted May 18th, 2005 [RS 813.112.1]. This Ordinance is based on the OECD Principles of Good Laboratory Practice, as revised in 1997 and adopted onNovember 26th, 1997 by decision ofthe OECD Council [C (97)186/Final]. There were no circumstances that may have affected the quality orintegrity ofthe data. StudyDirector: DrJens FrankeHarlan Laboratories Study C30920 Leuco Sulfur Black I Report 

## QUALITYASSURANCE GLP STATEMENT Harlan Laboratories Ltd., Zelgliweg 1, 4452 Itingen I Switzerland Harlan Laboratories Study: Test Item: Study Director: C30920 Leuco Sulfur Black I DrJens Franke Page6

Study Title: Determination ofthe Freezing Point 

### I Freezing Range The general facilities and activities are inspected at least once a year and the results are reported to the responsible person and the management. Study procedures were periodically inspected. The study plan and this report were audited by the Quality Assurance. The dates are given below. Dates ofReports to the Study Dates and Types ofQA Inspections Director and Test Facility Management December 16, 2008 Study plan December 16, 2008 January 06, 2009 Process based January 06, 2009 {Test performance) February 18, 2009 Report February 18, 2009 This statement also confirms that this final report reflects the raw data. Quality Assurance: Mr Ulrich Kofink

# ~~/A~ ..................................

# ~Harlan Laboratories Study C30920 Leuco Sulfur Black 1 

## PREFACE General Information Test Item: Study Title: Sponsor: Study Monitor: Test Facility: QA:



### Responsibilities Study Director: Deputy Study Director: Reporting: Technical Coordinator: HeadofQA: 

### Schedule Experimental Starting Date: Experimental Completion Date: Study Completion Date: Report Page 7



### Leuco Sulfur Black 1 Detennination ofthe Freezing Point I 

### Freezing Range Clariant Products (Switzerland) Ltd. Rothausstrasse 61 4132 Muttenz 1 I 

### Switzerland Dr Bruno Kunz Harlan Laboratories Ltd. Zelgliweg 1 

### 4452 Itingen I 

### Switzerland Harlan Laboratories Ltd. Quality Assurance GLP Zelgliweg 1 4452 Itingen I 

### Switzerland



### Dr Jens Franke Ms Mirjam Weissenfeld Ms Sabine Affolter Mr Gregor Czichy Mr Tobias Fink
January 12, 2009 January 13, 2009 February 24,2009Harlan Laboratories Study C30920 Leuco SulfurBlack I Report


### Data Requirements I

### Test Guidelines Page 8

This study followed the procedures indicated by the following internationally accepted guidelines and recommendations: • EEC Directive 92/69, Part A, Methods for the determination of physico-chemical properties, A.1 "Melting/Freezing temperature", EEC Publication No. L383, December 1992. • OECD Guideline for Testing ofChemicals No. 102, "Melting Point 

### I Melting Range", adopted July 27, 1995. • Council Regulation (EC) No. 440/2008, 30 May 2008, Part A, Methods for the determination ofphysico-chemical properties, A.1 "Melting/Freezing temperature" 

### Archiving Harlan Laboratories Ltd., 4452 Itingen/Switzerland will retain the study plan, raw data, a sample oftest item and the final report ofthe present study for at least ten years. No data will be discarded without the Sponsor's written consent. 

### Summary ofStudy Plan Amendments There were no amendments to the study plan.Harlan Laboratories Study C30920 Leuco SulfurBlack I 

## 1 SUMMARY Report Page9



### The freezing point of Leuco Sulfur Black 1 was determined to be -1.7 °C ± 

### 0.2 

# oc which is equal to 271.6 K ± 

### 0.2 K by visualjudgement.Harlan Laboratories Study C30920 Leuco Sulfur Black I 

## 2 PURPOSE Report Page 10



### The purpose ofthe study was to evaluate the freezing point I 

### freezing range ofthe test item.Harlan Laboratories Study C30920 Leuco SulfurBlack 1 Report 

## 3 MATERIALS AND METHODS 3.1 Test Item Data oftest item as supplied bythe Sponsor. Identification: Batch Number: Purity: Appearance: ExpiryDate: Storage Conditions: Leuco Sulfur Black 1 ESA0007595 

### 45.5% Paste Liquid July 11, 2011 At room temperature at about 20

# oc 3.2 Test System and Reagents Thermocouples Water from Harlan Laboratories supply Acetone Dry ice Page 11

Rationale: The test systems and test methods are recommended byinternational guidelines. 

### 3.3 Principle ofthe Test The above-mentioned guidelines contain several different methods for the determination ofthe freezing point 

### I freezing range. These are, among others, thermal analysis using a calorimeter and visual test (e.g. capillarymethod), where the melting orfreezing temperature, respectively, is measured. 

### In the present study a combination ofboth methods was applied. An amount oftest item was filled into a test tube and the probe ofa thermocouple was placed in the centre of the sample. The test item was cooled down under stirring until solidification occurred. The temperature/time curve 

### was recorded during the cooling of the test item. Additionally, the physical state was observed visually.Harlan Laboratories Study C30920 Leuco Sulfur Black l 

## 3.4 Performance ofthe Test 3.4.1 Preliminary Test Report Page 12

Some test item was filled in a small glass tube, which was stored for about 19 hours in a freezer at -22 °C. The physical state was observed visually. The test item was frozen after storage. This indicates that the freezing point ofLeuco Sulfur Black I must be above -22 °C. 

### 3.4.2 Main Test About 1 mL ofthe test item were filled in a test tube and cooled down using acetone and dry ice until solidification occurred. The probe ofa thermocouple was placed inthe centre ofthe sample. The temperature was measured with an appropriate thermocouple. The test was carried out in duplicate. The temperature/time curves were recorded during the cooling of the test item. Additionally, the physical state was observed visually.Harlan Laboratories Study C30920 Leuco Sulfur Black 1 

### 3.5 Data Handling Report Page 13



### The freezing point is defined as the temperature at which phase transition from liquid to solid state at normal atmospheric pressure takes place. This temperature ideally corresponds to the temperature at the melting point. As the phase transition ofmany substances takes place over a large temperature range, it is often described as the freezing respectivelymelting range. If the difference between the temperature at the beginning and at the final stage of melting/freezing is within 1 

### K, the temperature at the beginning ofmelting/freezing is taken as the freezing point, otherwise the two temperatures will be reported. Results will be given in degrees Centigrade and in Kelvin. Results 

### are given in degrees centigrade and 

### in Kelvin. Conversion ofunits

# ec to K): t 

### = T- 273.2 with t 

## = Celsius temperature, degrees Centigrade [0C] 

### T Thermodynamic temperature, Kelvin [K]Harlan Laboratories Study C30920 Leuco SulfurBlack 1 

## 4 RESULTS Report Page 14

The determination ofthe freezing point 

### I freezing range ofthe test item was performed according to the EEC Directive 92169, December 1992 and Council Regulation (EC) No. 44012008, A.l "Melting/Freezing temperature" and to the OECD Guideline No. 102: "Melting point 

### I melting range", adopted July27, 1995. A preliminary test wasperformed to check the approximate freezing temperature ofLeuco Sulfur Black 1. Thetest item was stored about 19 hours at -22 °C in a freezer. As the sample was frozen after this time the freezing temperature ofLeuco Sulfur Black 1is above -22 °C. During the main tests, about 1 mL ofthe test item placed in a small test tube were cooled down from room temperature to about -2 °C using a dry ice and acetone mixture. At -1.8 °C (1st test) and -1.5 

# oc (2nd test), respectively, the test item was frozen by visual judgement. The results ofthe individual measurements are summarized in Table 1.Harlan Laboratories Study C30920 Leuco SulfurBlack I 

## 5 CONCLUSIONS Report



### The aim ofthis study was to determine the freezing point/range ofLeuco SulfurBlack 

### 1. The freezing point ofLeuco Sulfur Black 1was determined to be -1.7 

# oc ± 

### 0.2 

# oc which is equal to 271.7 K± 

### 0.2 K. Page 15Harlan Laboratories Study C30920 Leuco SulfurBlack 1 

## 6 TABLES Report

Table 1 Detennination ofthe FreezingPoint ofLeuco Sulfur Black 1 (Summary) Freezing Point 

## roq [K] Preliminarytest Above 

### -22 °C Above 

### 251.2 1 81 main test -1.8 

### 271.4 2nd main test -1.5 

### 271.7 Mean value 

### -1.7 271.6 Standard deviation(±) 

### 0.2 0.2 The mean freezing point was calculated from the bold values.



## CONTAINS NO CBI 

# I '**PH~** (.:;l:J.7jr"L Page 16