1、April 2011 Translation by DIN-Sprachendienst.English price group 7No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 5
2、9.140.30!$neq“1756678www.din.deDDIN EN ISO 13365Leather Chemical tests Determination of the preservative (TCMTB, PCMC, OPP, OIT) content inleather by liquid chromatography (ISO 13365:2011)English translation of DIN EN ISO 13365:2011-04Leder Chemische Prfungen Bestimmung von Konservierungsmitteln (TC
3、MTB, CMK, OPP, OIT) in Leder mittelsFlssigchromatographie (ISO 13365:2011)Englische bersetzung von DIN EN ISO 13365:2011-04Cuir Essais chimiques Dosage des agents de conservation (TCMTB, PCMC, OPP, OIT) dans le cuir parchromatographie en phase liquide (ISO 13365:2011)Traduction anglaise de DIN EN IS
4、O 13365:2011-04www.beuth.deIn case of doubt, the German-language original shall be considered authoritative.Document comprises 9 pages03.11 DIN EN 13365:2011-04 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee CEN/TC 289 “Leather” (Secre
5、tariat: UNI, Italy) in collaboration with Technical Committee IULTCS “International Union of Leather Technologists and Chemists Societies”. The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062
6、-05-52 AA Chemische Prfverfahren fr Leder. This document is based on the method specified in IUC 29 of IULTCS. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 2418 DIN EN ISO 2418 ISO 4044 DIN EN ISO 4044 ISO 4684 DIN EN ISO 4684 Nation
7、al Annex NA (informative) Bibliography DIN EN ISO 2418, Leather Chemical, physical and mechanical and fastness tests Sampling location DIN EN ISO 4044, Leather Chemical tests Preparation of chemical test samples DIN EN ISO 4684, Leather Chemical tests Determination of volatile matter 2 EUROPEAN STAN
8、DARD NORME EUROPENNE EUROPISCHE NORM EN ISO 13365 January 2011 ICS 59.140.30 English Version Leather - Chemical tests - Determination of the preservative (TCMTB, PCMC, OPP, OIT) content in leather by liquid chromatography (ISO 13365:2011) Cuir - Essais chimiques - Dosage des agents de conservation (
9、TCMTB, PCMC, OPP, OIT) dans le cuir par chromatographie en phase liquid (ISO 13365:2011) Leder - Chemische Prfungen - Bestimmung von Konservierungsmitteln (TCMTB, CMK, OPP, OIT) in Leder mittels Flssigchromatographie (ISO 13365:2011) This European Standard was approved by CEN on 14 January 2011. CEN
10、 members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on appl
11、ication to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Ma
12、nagement Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Neth
13、erlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation
14、 in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 13365:2011: EForeword This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by July 2011, and conflicting national
15、 standards shall be withdrawn at the latest by July 2011. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC
16、 Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
17、Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. 2DIN EN ISO 13365:2011-04 EN ISO 13365:2010 (E) This document (EN ISO 13365:2011) has been prepared by Technical Committee CEN/TC 289 “Leather”, the secretariat o
18、f which is held by UNI, in collaboration with Technical Committee IULTCS “International Union of Leather Technologists and Chemists Societies”. 1 Scope This International Standard specifies a test method for the determination of the content of the following preservative agents: g127 2-(thiocyanometh
19、ylthio)-benzothiazole (TCMTB); g127 4-chloro-3-methylphenol (PCMC); g127 2-phenylphenol (OPP); g127 2-octylisothiazol-3(2H)-one (OIT); in leather by liquid chromatography. Preservative agents are necessary to protect leather from microbiological attack. NOTE The preservative agents 4-chloro-3-methyl
20、phenol (PCMC) and 2-phenylphenol (OPP) can also be determined according to ISO 17070 and quantified by means of gas chromatography/mass spectroscopy (GC/MS). 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only t
21、he edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 2418, Leather Chemical, physical and mechanical and fastness tests Sampling location ISO 4044, Leather Chemical tests Preparation of chemical test samples ISO 4684,
22、 Leather Chemical tests Determination of volatile matter 3 Principle The leather sample is extracted with a suitable solvent using ultrasonic waves. The filtered extract is analysed by high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection. 4 Reagents 4.1 TCMTB, minimum 99,7 %
23、. 4.2 TCMTB stock solution, 500 mg/l in acetonitrile. 3DIN EN ISO 13365:2011-04 EN ISO 13365:2010 (E) 4.3 PCMC, minimum 99,5 %. 4.4 PCMC stock solution, 500 mg/l in acetonitrile. 4.5 OPP, minimum 99,5 %. 4.6 OPP stock solution, 500 mg/l in acetonitrile. 4.7 OIT, minimum 97,0 %. 4.8 OIT stock solutio
24、n, 500 mg/l in acetonitrile. 4.9 Acetonitrile, HPLC grade. 4.10 Water, HPLC grade. 5 Apparatus and materials Usual laboratory apparatus is required and, in particular, the following. 5.1 Analytical balance, weighing to an accuracy of 0,1 mg. 5.2 HPLC system, with UV detection or other suitable detec
25、tors. 5.3 Separation column, reversed phase C8 or C18 with corresponding pre-column. 5.4 Ultrasonic bath, e.g. 40 kHz. 5.5 Membrane filter, polyamide, 0,45 m. 6 Procedure 6.1 Sampling and sample preparation If possible, sample in accordance with ISO 2418 and grind in accordance with ISO 4044. If sam
26、pling in accordance with ISO 2418 is not possible (e.g. leathers from finished products, such as shoes or garments), details of the sampling shall be given, together with the test report. Wet intermediates like wet blue and wet white shall be dried as described in ISO 4044 prior to grinding. 6.2 Pre
27、paration of analytical solution Weigh (1 g114 0,01) g of ground leather to the nearest 0,001 g in a 100 ml conical flask. Pipette 20 ml of acetonitrile (4.9) and add it to the leather. The leather sample is extracted in an ultrasonic bath (5.4) for 1 h g114 5 min (80 % ultrasound power) at room temp
28、erature. During extraction, the temperature in the mixture increases to about 35 C. Subsequently, a part of the extract is filtered through a membrane filter (5.5) into a suitable vial. The filtrate is analysed by HPLC (5.2) and detected preservatives are quantified. 4DIN EN ISO 13365:2011-04 EN ISO
29、 13365:2010 (E) 6.3 Chromatographic conditions Proposal: Separation column: reversed-phase (RP) column (C18 HD, 250 mm/4 mm, 100 , 5 m) with pre-column Flow rate: 0,8 ml/min Mobile phase: A: water, B: acetonitrile Gradient: 60 % B for 6 min isocratic, then linear to 95 % B in 9 min Column oven: 30 C
30、 UV detection: 275 nm Injection volume: 20 l 6.4 Calibration Calibration is carried out by means of an external standard. Prepare adequate dilutions (in acetonitrile) of preservative stock solutions (4.2, 4.4, 4.6 and 4.8). Calibration shall be done using at least six concentration levels. The calib
31、ration is effected by plotting a graph of the preservative peak area versus its concentration, in micrograms per millilitre (g/ml). As very different preservative concentrations can be expected, it is not possible to cover the whole range with a single calibration curve. 7 Calculation Calculate the
32、mass fraction, wi, of every preservative detected, in milligrams per kilogram (mg/kg) of leather, using the following equation: i10001000VFwmg85 g152g152g117g32g117where wiis the mass fraction, expressed in milligrams per kilogram (mg/kg), of a certain preservative in leather; g85 is the mass concen
33、tration of preservative obtained from the calibration, in micrograms per millilitre (g/ml); V is the extract volume, in millilitres (ml); F is the dilution factor; m is the quantity of sample weighed, in grams (g). The mass fraction of each preservative is given in milligrams per kilogram (mg/kg), r
34、ounded to the nearest 0,1 mg. 5DIN EN ISO 13365:2011-04 EN ISO 13365:2010 (E) The mass fraction of preservative referred to dry matter, according to ISO 4684, can be calculated using the following equation: dmwwDg32g152 where wdmis the mass fraction of preservative, expressed in milligrams per kilog
35、ram (mg/kg), of sample referred to dry matter; w is the mass fraction of preservative, expressed in milligrams per kilogram (mg/kg), of the sample being tested; D is the recalculation factor for dry matter v100100Dwg32g16wvis the mass fraction of volatile matter, based on ISO 4684, expressed as a pe
36、rcentage. 8 Test report The test report shall include the following information: a) a reference to this International Standard, i.e. ISO 13365:2011; b) the type, origin and designation of the analysed product and the sampling method used; c) the type of liquid chromatography detection; d) the analyt
37、ical result for each mass fraction of preservative, in milligrams per kilogram (mg/kg) rounded to one decimal place; e) any deviation from the analytical procedure. 6DIN EN ISO 13365:2011-04 EN ISO 13365:2010 (E) Bibliography 1 ISO 17070, Leather Chemical tests Determination of pentachlorophenol content 7DIN EN ISO 13365:2011-04 EN ISO 13365:2010 (E)
