DISCLAIMER 

This report is the property of Clariant. 

Its content is confidential and not for general 

release. It is not allowed to cite and reveal the report or its 

content to a third party without prior written approval of 

Clariant. 

REPORT 

Leu co Sulfur Black 1 

9~515B 

harlanTM 

... 

Determination of the Freezing Point I Freezing 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 

Dr Jens 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 

Data Requirements I Test Guidelines .................................................................................... 8 

Archiving ............................................................................................................................... 8 

Summary of Study Plan 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 ofthe Test ............................................................................................... 11 

3.4 Performance of the Test ......................................................................................... 12 

3.4.1 Preliminary Test ...................................................................................... 12 

3.4.2 Main Test ................................................................................................. 12 

3.5 Data Handling ........................................................................................................ 13 

4 RESULTS ............................................................................................................................ 14 

5 CONCLUSIONS ................................................................................................................. 15 

6 TABLES .............................................................................................................................. 16 

LIST OF TABLES 

Table 1 Determination of the Freezing Point of Leuco Sulfur Black 1 

(Summary) .................................................................................................................. 16 

J' '. .,_,.~.. ,... • 
Harlan Laboratories Study C30920 

Leuco Sulfur Black 1 

GLP CERTIFICATE 

Report 

fl'll SchweiZerischt lldgenossenschoh Fedtlll DoportmtAI of Homt Affol" DHA 

y Conl6dlrlllon 

ConftderuioM 

sulut 

Svfner• 

-.. Offkool,....lfoiiiiiPOPII ~ Conftdtruiun svizra Fedtrel DepartmeM of tht iawltonment. sw1ssmedic Tron-t EntrtY ond Communi- DlTIC 

Swlu Conftderotlon -.. -fvrlhe flwi-PODI 

Statement of GLP Compliance 

According to Article 14 paragraph 3 Ordinance on Good Laboratory Plac:llce (OGLP, SR 813.112.1) 

The notification euthority tor chemlcals conftnns that the foDowing test facility was inspected with 

respect to the compnance with 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 

of the test facility. 

Harlan Laboratories Ltd. 

lelgllweg 1 

4452 ltingen, Switzerland. 

Areas of expertise according to 

article 3 paragraph 1 letter d OGLP: 

1 J Physical-chemical testing, 

21 Tox!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 J Studies on eff8cts on mesocosms and 

natural ecosystems, 

81 Analytical and clnlcal chemistry tasting, 

9.1 Other studies (safety pharmacology and 

animal metabolism). 

Inspection authority: Federal Office for the Environment (FOEN) 1 Federal Office of Public Heelth 

(FOPH) I Swiss Agency for Therapeutic Products (Swlssmedic) 

Date of Inspection: 05th to 09111 and 26th to 30th November 2007 

Date of dec: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 2 OGLP. 

lbo __ ,., ..... _ ... ____ ,., ..... __,,_IGU')Iorhi'OEH, ... ,OI'H ... _ 

-F-O!IIo..,IP ___ ,_ __ .......,IDr_C_Iom. 

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Page 3 
Harlan Laboratories Study C30920 

Leuco Sulfur Black 1 

SIGNATURES 

Study Director: 

Management: 

Report Page4 

Dr J ens Franke 

::f!;( Dr Jom 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: 

Study Director: 

C30920 

Leuco Sulfur Black 1 

Dr Jens Franke 

Page 5 

Study Title: Determination of the Freezing Point I Freezing Range 

This study has 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 on November 26th, 1997 by decision of the OECD Council [C (97)186/Final]. 

There were no circumstances that may have affected the quality or integrity of the data. 

Study Director: Dr Jens Franke 
Harlan Laboratories Study C30920 

Leuco Sulfur Black I 

Report 

QUALITY ASSURANCE GLP STATEMENT 

Harlan Laboratories Ltd., Zelgliweg 1, 4452 Itingen I Switzerland 

Harlan Laboratories Study: 

Test Item: 

Study Director: 

C30920 

Leuco Sulfur Black I 

Dr Jens Franke 

Page6 

Study Title: Determination of the 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 of Reports to the Study 

Dates and Types of QA 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 of the 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 24,2009 
Harlan Laboratories Study C30920 

Leu co Sulfur Black 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 of Chemicals 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 of physico-chemical properties, A.1 "Melting/Freezing temperature" 

Archiving 

Harlan Laboratories Ltd., 4452 Itingen/Switzerland will retain the study plan, raw data, a sample 

of test item and the final report of the present study for at least ten years. 

No data will be discarded without the Sponsor's written consent. 

Summary of Study Plan Amendments 

There were no amendments to the study plan. 
Harlan Laboratories Study C30920 

Leuco Sulfur Black 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 visual judgement. 
Harlan Laboratories Study C30920 

Leuco Sulfur Black I 

2 PURPOSE 

Report Page 10 

The purpose of the study was to evaluate the freezing point I freezing range of the test item. 
Harlan Laboratories Study C30920 

Leuco Sulfur Black 1 

Report 

3 MATERIALS AND METHODS 

3.1 Test Item 

Data of test item as supplied by the Sponsor. 

Identification: 

Batch Number: 

Purity: 

Appearance: 

Expiry Date: 

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 by international guidelines. 

3.3 Principle of the Test 

The above-mentioned guidelines contain several different methods for the determination of the 

freezing point I freezing range. These are, among others, thermal analysis using a calorimeter 

and visual test (e.g. capillary method), where the melting or freezing temperature, respectively, is 

measured. In the present study a combination of both methods was applied. 

An amount of test item was filled into a test tube and the probe of a 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 of the 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 of the test item were filled in a test tube and cooled down using acetone and dry ice 

until solidification occurred. The probe of a thermocouple was placed in the centre of the 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 of many substances takes place over a 

large temperature range, it is often described as the freezing respectively melting 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 of melting/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 [

0 C] 

T Thermodynamic temperature, Kelvin [K] 
Harlan Laboratories Study C30920 

Leuco Sulfur Black 1 

4 RESULTS 

Report Page 14 

The determination of the freezing point I freezing range of the 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 July 27, 1995. 

A preliminary test was performed to check the approximate freezing temperature of Leuco Sulfur 

Black 1. The test 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 1 is above -22 °C. 

During the main tests, about 1 mL of the 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 Sulfur Black I 

5 CONCLUSIONS 

Report 

The aim of this study was to determine the freezing point/range ofLeuco Sulfur Black 1. 

The freezing point of Leuco Sulfur Black 1 was determined to be 

-1.7 oc ± 0.2 oc 

which is equal to 271.7 K ± 0.2 K. 

Page 15 
Harlan Laboratories Study C30920 

Leuco Sulfur Black 1 

6 TABLES 

Report 

Table 1 Detennination of the Freezing Point ofLeuco Sulfur Black 1 (Summary) 

Freezing Point 

roq [K] 

Preliminary test 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