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net

ICS 59.140.30
Y 46

National Standard of the People’s Republic of China

GB/T 19942-2019
Replaces GB/T 19942-2005

Leather and fur—Chemical tests—

Determination of banned azo colorants
皮革和毛皮 化学试验 禁用偶氮染料的测定

(ISO 17234-1:2015, Leather—Chemical tests for the determination of certain azo

colorants in dyed leathers—Part 1: Determination of certain aromatic amines
derived from azo colorants, MOD)

(English Translation)

Issue date: 2019-12-31 Implementation date: 2020-07-01

Issued by the State Administration for Market Regulation
the Standardization Administration of the People’s Republic
of China

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Contents

Foreword ............................................................................................................................... i
1 Scope ............................................................................................................................. 1
2 Normative references ..................................................................................................... 1
3 Terms and definitions ..................................................................................................... 1
4 Principle.......................................................................................................................... 2
5 Reagents and materials ................................................................................................. 3
6 Apparatus ....................................................................................................................... 4
7 Sampling and preparation of specimens ....................................................................... 5
8 Test procedure................................................................................................................ 5
9 Calculation and expression of results ............................................................................ 7
10 Feasibility of the method .............................................................................................. 8
11 Test report..................................................................................................................... 8
Annex A (Informative) Structural changes of this standard with reference to ISO
17234-1:2015 ....................................................................................................................... 9
Annex B (Informative) Technical differences between this standard and ISO
17234-1:2015, and justification.......................................................................................... 10
Annex C (Informative) Chromatographic analyses ......................................................... 12

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Foreword

ChinaStandards.net is in charge of this English translation. In case of any doubt about

the English translation, the Chinese original shall be considered authoritative.

This standard is developed in accordance with the rules given in GB/T 1.1-2009.

This standard replaces GB/T 19942-2005 Leather and fur—Chemical

tests—Determination of banned azo colorants.

Main technical changes have been made as follows, with respect to GB/T 19942-2005:

—The reference to the year of GB/T 6682 has been removed from and reference to “GB/T
33392” has been introduced to the normative references (see Clause 2; Clause 2 of 2005
edition);

—The specific test conditions have been removed from and an amine determination
method has been introduced to the clause of “Principle” (see Clause 4; Clause 4 of 2005
edition);

—A requirement for methanol purity has been introduced (see 5.2);

—Ethyl acetate has been introduced (see 5.3);

—A purity requirement and explanatory note for t-butyl methyl ether have been introduced
(see 5.4);

—A requirement for the standing time of prepared sodium dithionite solution has been
introduced (see 5.6);

—The preheated temperature requirement for citrate buffer solution (see 5.11; 6.9 of 2005
edition);

—The types of chromatographic equipment have been modified in the clause “Apparatus”
(see 6.12; 5.11 of 2005 edition);

—A requirement for sampling in the case of patchwork fabrics with varicolored patterns,
various leather and fur qualities has been introduced (see 7.1);

—A range of room temperature for reductive cleavage has been introduced (see 8.2);

—A filter process before chromatographic analysis has been introduced to liquid-liquid

extraction (see 8.3);

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—A requirement that analysis of standard solution for process control shall be carried out
with each batch of specimens has been introduced (see 8.5; Clause 9 of 2005 edition);

—The chromatographic analysis parameters have been moved to Annex C and

parameters for liquid chromatography have been introduced (see Annex C; 10.1 of 2005
edition);

—The symbols in calculation formula have been modified (see clause 9; clause 11 of
2005 edition);

—“Feasibility of the method” has been moved to Clause 10 and a description for aromatic
amines numbers 5, 6, and 22 have been introduced (see Clause 10; 8.4 of 2005 edition);

—The contents of test report have been modified (see Clause 11; Clause 12 of 2005
edition).

This standard is a redraft based on modified adoption of ISO 17234-1:2015

Leather—Chemical tests for the determination of certain azo colorants in dyed
leathers—Part 1: Determination of certain aromatic amines derived from azo colorants.

This standard is changed largely from ISO 17234-1:2015 in terms of structure. See Annex
A for cross references to the clauses/subclauses between this standard and ISO
17234-1:2015.

Technical differences have been made in this standard with respect to cross reference,
and have been listed together with the justification in Annex B.

For the convenience of users, this standard includes editorial changes as follows:

—The standard name has been changed to Leather and fur—Chemical

tests—Determination of banned azo colorants;

—The example of the suitable product type in the note of “6.5 Polypropylene or glass
column” of ISO17234-1: 2015 has been removed and a note of commercially available
column has been introduced;

—A note has been introduced to “7.2 t-butyl methyl ether” of ISO 17234-1: 2015;

—A note “if the detected amount ... is over 30 mg/kg, it shall be assumed that the
specimen submitted has been manufactured or treated using a certain banned azo
colorants was used” has been introduced to 9.2;

—A GC/MS total ion chromatogram of aromatic amine reference has been introduced to

ii

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Annex A of ISO 17234-1:2015;

—Annex B and Annex C of ISO 17234-1:2015 have been removed.

This standard was proposed by the China National Light Industry Council.

This standard is under the jurisdiction of the National Technical Committee on Leather of
Standardization Administration of China (SAC/TC 252).

The previous edition of this standard is as follows:

—GB/T 19942-2005.

iii

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Leather and fur—Chemical tests—

Determination of banned azo colorants

Warning: Users of this standard shall be experienced in normal laboratory

practicing. Aromatic amines are classified as substances known to be or suspected
to be human carcinogens. This standard does not purport to address possible
safety issues exhaustively. It is the user’s responsibility to use safe and proper
techniques and guarantee compliance with the appropriate national and local laws
and regulations.

1 Scope

This standard specifies a method for determining banned azo colorants, which can
release carcinogenic aromatic amines, derived from dyed leather and fur.

This standard applies to the determination of banned azo colorants in various dyed
leathers, furs and their products.

2 Normative references

The following referenced documents are indispensable for the application of this
document. For dated references, only the edition cited applies. For undated references,
the latest edition of the referenced document (including any amendments) applies.

GB/T 6682 Water for analytical laboratory use—Specification and test methods (GB/T
6682-2008, ISO 3696:1987, MOD)
GB/T 33392 Leather and fur—Chemical tests—Determination of 4-aminoazobenzene in
banned azo colorants (GB/T 33392-2016, ISO 17234-2:2011, MOD)
QB/T 1267 Fur—Chemical, physical and mechanical and fastness tests—Sampling
location (QB/T 1267-2012, ISO 2418:2002, MOD)
QB/T 1272 Fur—Preparation of chemical test samples (QB/T 1272-2012, ISO
4044:2008, MOD)
QB/T 2706 Leather—Chemical, physical and mechanical and fastness
tests—Sampling location (QB/T 2706-2005, ISO 2418:2002, MOD)
QB/T 2716 Leather—Preparation of chemical test samples (QB/T 2716-2018, ISO
4044:2008, MOD)

3 Terms and definitions

For the purposes of this document, the following terms and definitions apply.

3.1

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banned azo colorants

colorants that can release, by reductive cleavage of azo group(s), one or more of the
aromatic amines listed in Table 1

Table 1 24 carcinogenic aromatic amines

No. Aromatic amine CAS No.
1 4-aminodiphenyl 92-67-1
2 benzidine 92-87-5
3 4-chloro-o-toluidine 95-69-2
4 2-naphthylamine 91-59-8
a
5 2-aminoazotoluene 97-56-3
a
6 2-amino-4-nitrotoluene 99-55-8
7 p-chloroaniline 106-47-8
8 2,4-diaminoanisole 615-05-4
9 4,4'-diaminodiphenylmethane 101-77-9
10 3,3'-dichlorobenzidine 91-94-1
11 3,3'-dimethoxybenzidine 119-90-4
12 3,3'-dimethylbenzidine 119-93-7
13 3,3'-dimethyl-4,4'-diaminodiphenylmethane 838-88-0
14 p-cresidine 120-71-8
15 4,4'-methylene-bis-(2-chloroaniline) 101-14-4
16 4,4'-oxydianiline 101-80-4
17 4,4'-thiodianiline 139-65-1
18 o-toluidine 95-53-4
19 2,4-toluylenediamine 95-80-7
20 2,4,5-trimethylaniline 137-17-7
21 2-anisidine 90-04-0
22b 4-aminoazobenzene 60-09-3
23 2,4-xylidine 95-68-1
24 2,6-xylidine 87-62-7
a
As shown by this method, 2-aminoazotoluene (CAS-number 97-56-3, No. 5) and
2-amino-4-nitrotoluene (CAS-number 99-55-8, No. 6) are further reduced to o-toluidine (CAS-number
95-53-4, No. 18) and 2,4-toluylenediamine (CAS-number 95-80-7, No. 19).
b
As shown by this method, 4-aminoazobenzene (No. 22, CAS number 60-09-3) is able to form aniline
and/or 1,4-phenylenediamine. The presence of aniline and/or 1,4-phenylenediamine shall necessitate a
retest using GB/T 33392.

4 Principle

After degreasing, the specimen is treated with sodium dithionite in an aqueous buffer
solution (specified pH) at a certain temperature in a closed vessel. The aromatic amines
released in the process of reductive cleavage are transferred to a t-butyl methyl ether
phase by means of liquid-liquid extraction using Kieselgur columns. The t-butyl methyl
2

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ether extract is then concentrated and the residue is dissolved in a suitable solvent until
volume is made up. Determination of the amines is performed by means of
high-performance liquid chromatography (HPLC) using a diode array detector (DAD) or
mass selective detector (HPLC/MS), capillary gas chromatography with a mass-selective
detector (GC-MS) or by capillary electrophoresis with a diode array detector (CE/DAD), or
qualitatively with thin layer chromatography (TLC, HPTLC).

The amines shall be identified by means of at least two different chromatographic

separation methods in order to avoid any possible misinterpretations caused by interfering
substances (such as position isomers of the amines to be identified) and hence any
incorrect statements. Amine quantification shall be performed by HPLC/DAD or GC/MS.

5 Reagents and materials

Use only reagents of recognized analytical grade, unless otherwise stated. All solutions
are aqueous solutions.

5.1 Water, Grade 3 according to GB/T 6682, for test purpose.

5.2 Methanol: Chromatographic grade.

5.3 Ethyl acetate: Chromatographic grade.

5.4 t-butyl methyl ether: Analytical grade.

Note: t-butyl methyl ether of analytical grade may contain impurities that can react with the aromatic
amines released in the process of reductive cleavage, resulting in detection failure or undervaluation of a
positive specimen. It is recommended to evaporate t-butyl methyl ether for purification before use, or to
use reagent of chromatographic grade.

5.5 Sodium dithionite, minimum 87% purity.

5.6 Aqueous sodium dithionite solution, 200 mg/ml, freshly prepared, to be used
immediately after resting for 1 h in a closed vessel.

5.7 n-hexane.

5.8 Aromatic amine standards: listed in Table 1 (highest available purity standard).

5.9 Stock solution of the amines (5.8): 400 mg/l in ethyl acetate for TLC.

5.10 Stock solution of the amines (5.8): 200 mg/l in methanol for GC, HPLC, CE.

5.11 Citrate buffer solution, 0.06 mol/l, pH = 6, preheated to (70 ± 5) °C.

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5.12 Standard solution for amine process control: 30 µg amine per milliliter solvent,
freshly prepared from stock solutions 5.9 or 5.10 depending on the analytical method.

5.13 20% methanolic NaOH solution, 20 g NaOH dissolved in 100 ml methanol.

6 Apparatus

6.1 Suitable reaction vessel, of temperature-resistant glass with a gas-tight closure.

6.2 Hot cabinet with sand bath (sea sand, 0.1 mm to 0.3 mm) or water bath with
thermostat.

6.3 Thermometer, 0.5 °C accuracy at 70 °C.

6.4 Volumetric flasks, different volumes.

6.5 Polypropylene or glass column with 25 mm to 30 mm inner diameter and 140 mm to

150 mm length, glass filter at the outlet, filled with porous granulated Kieselgur (about 20 g,
packed solidly by tapping the column).

Note: Products available commercially may be used.

6.6 Polypropylene or polyethylene syringe, 2 ml.

6.7 Vacuum rotary evaporator with vacuum control and water bath.

6.8 Pipettes, 10 ml, 5 ml, 2 ml, 1 ml.

6.9 Ultrasonic bath with thermostat.

6.10 Round-bottomed flask, of 100 ml with standard ground joint.

6.11 Balance, accuracy of 0.1 mg.

6.12 Chromatographic equipment selected from the following:

—High performance liquid chromatography (HPLC) with gradient controller and DAD
or MS detector.

—Capillary gas chromatography (GC) with mass selective detector (MS).

—Capillary electrophoresis (CE) with DAD.

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