HJ 507-2009_English: PDF (HJ507-2009)
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Technical requirement for environmental labeling products. Leather and synthetic leather
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HJ 507-2009
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| Standard ID | HJ 507-2009 (HJ507-2009) | | Description (Translated English) | Technical requirement for environmental labeling products. Leather and synthetic leather | | Sector / Industry | Environmental Protection Industry Standard | | Classification of Chinese Standard | Y46 | | Classification of International Standard | 59.140.30 | | Word Count Estimation | 16,161 | | Date of Issue | 2009-10-30 | | Date of Implementation | 2010-01-01 | | Quoted Standard | GB/T 19941-2005; GB/T 19942-2005; GB/T 20384-2006; GB/T 20386-2006; GB/T 22807-2008; GB/T 22808-2008; GB/T 22930-2008; GB/T 22932-2008; QB/T 2724-2005; QB/T 2725-2005 | | Drafting Organization | Ministry of Environmental Protection and Development Center | | Administrative Organization | Ministry of Environment Protection | | Regulation (derived from) | Department of Environmental Protection Notice No. 56 of 2009 | | Summary | This standard specifies the leather and synthetic leather for environmental labeling products terminology and definitions, product classification, the basic requirements, technical contents and test method. This standard applies to leather and polyurethane synthetic leather. | HJ 507-2009
Technical requirement for environmental labeling products.Leather and synthetic leather
HJ
National Environmental Protection Standard of the People's Republic
Environmental labeling products technical requirements leather and synthetic leather
Technical requirement for environmental labeling products
-Leather and synthetic leather
2009-10-30 Approved.2010-01-01 Implementation
Ministry of Environmental Protection released
Ministry of Environmental Protection
announcement
No. 56 of.2009
In order to implement the Environmental Protection Law of the People's Republic of China, protect the environment, protect human health, and promote scientific and technological progress, the environment is now approved.
Two standards, such as the technical requirements for logo products, leather and synthetic leather, are national environmental protection standards and are released.
The standard name and number are as follows.
Second, environmental labeling products technical requirements heating radiator (HJ 508-2009)
The above standards have been implemented since January 1,.2010 and published by the China Environmental Science Press. The standard content can be found on the website of the Ministry of Environmental Protection.
Special announcement.
October 30,.2009
Content
Foreword..iv
1 Scope..1
2 Normative references..1
3 Terms and Definitions.1
4 Product Categories..1
5 Basic requirements..2
6 Technical content..2
7 Inspection method..3
Appendix A (Normative) Aromatic amines that are not allowed to decompose from dye under reducing conditions..4
Appendix B (Normative) Chlorinated Benzene and Chlorinated Toluene..5
Appendix C (Normative Appendix) Dyes recognized as carcinogenic.6
Appendix D (Normative) Dyestuffs identified as sensitizing.7
Appendix E (Normative) Determination of odor of synthetic leather 8
Appendix F (Normative) Determination of volatile organic compound (VOC) content 9
Foreword
To implement the Environmental Protection Law of the People's Republic of China, reduce the environmental and human body during the production and use of leather and synthetic leather products.
The impact of health, the development of this standard.
The standard values of pH and dilution in leather and synthetic leather products, free formaldehyde, extractable heavy metals, chlorophenols, ortho-benzene
Residues such as phenols, dyes and odors that can decompose carcinogenic aromatic amines, and volatile organic compounds in synthetic leather products
Compounds, organotin compounds, chlorinated benzene and chlorinated toluene impose restrictions on the toxic and hazardous substances in production chemicals.
With requirements.
This standard applies to China Environmental Labeling Product Certification.
This standard was formulated by the Science and Technology Standards Department of the Ministry of Environmental Protection.
This standard is mainly drafted by. Environmental Development Center of the Ministry of Environmental Protection, China Leather and Footwear Industry Research Institute, Hebei Dongming Industrial Group
Co., Ltd., Wenzhou Huanghe Leather Co., Ltd., Xingye Leather Technology Co., Ltd., Quanzhou Xinde Leather Co., Ltd., Zhejiang Volkswagen
Industry Co., Ltd., Fengan Leather Industry Co., Ltd., Gansu Hongliang Leather Industry Co., Ltd., Zibo Daheng Jiubao En Leather Group Co., Ltd.
Menxixin Microfiber Materials Co., Ltd., Anhui Anli Synthetic Leather Co., Ltd., Wenzhou Huafeng Artificial Leather Co., Ltd., Jinjiang, Fujian
Yuhua Microfiber Industrial Co., Ltd.
This standard was approved by the Ministry of Environmental Protection on October 30,.2009.
This standard has been implemented since January 1,.2010.
This standard is explained by the Ministry of Environmental Protection.
Iv
Environmental labeling products technical requirements leather and synthetic leather
1 Scope of application
This standard specifies the terms and definitions of leather and synthetic leather environmental labeling products, product classification, basic requirements, technical content and inspection party.
law.
This standard applies to leather and polyurethane synthetic leather.
2 Normative references
The contents of this standard refer to the terms in the following documents. For undated references, the valid version applies to this standard.
GB/T.19941-2005 Determination of formaldehyde content in leather and fur chemical tests
GB/T.19942-2005 Determination of banned azo dyes in leather and fur chemical tests
GB/T 20384-2006 Determination of residual chlorinated benzene and chlorinated toluene
GB/T 20386-2006 Determination of o-phenylphenol in textiles
GB/T 22807-2008 Determination of hexavalent chromium content in leather and fur chemical tests
GB/T 22808-2008 Determination of the content of pentachlorophenol in the chemical test of leather and fur
GB/T 22930-2008 Determination of heavy metal content in leather and fur chemical tests
GB/T 22932-2008 Determination of organotin compounds for chemical testing of leather and fur
QB/T 2724-2005 Determination of pH in leather chemistry test
QB/T 2725-2005 Determination of leather odour
3 Terms and definitions
The following terms and definitions apply to this standard.
3.1 Leather Leather
A product with performance properties made from animal skin and processed through a series of chemical treatments and mechanical processes.
3.2 Synthetic leather synthetic leather
Made of woven fabric, impregnated with polyurethane resin, dried or post-treated, similar to leather structure and
Products with physical and mechanical properties.
3.3 volatile organic compounds
Analysis by gas chromatography on a non-polar column, retention time between n-hexane and n-hexadecane, and known and unknown waves including them
Hairy organic compounds.
4 Product Categories
Products are classified into the following three categories according to their end use.
Class A. Baby products for infants and young children aged 36 months and below.
Class B. Direct contact with skin products, where most of the surface of the skin is in direct contact with human skin when worn or used.
Class C. Non-direct contact with skin products, when in wear or use, does not directly contact the skin or a small part of its surface and human skin.
direct contact.
5 basic requirements
5.1 Product quality should meet the requirements of their respective quality standards.
5.2 Pollutant emissions from product manufacturing enterprises shall comply with the requirements of national or local pollutant discharge standards.
5.3 Product manufacturers should focus on strengthening cleaner production in the production process.
6 Technical content
6.1 The limits of hazardous substances in products shall comply with the requirements of Table 1.
Table 1 Limits of hazardous substances in products
Classification item
Class A, Class B, Class C
pH 3.5～7.5 3.5～9.0
pH dilution difference ≤0.7 (detect this when pH< 4.0)
Free formaldehyde/(mg/kg) ≤ 20.0 ≤ 75.0 ≤ 150.0
Hexavalent chromium (Cr6) ≤5.0
Cadmium (Cd) ≤ 0.1
Mercury (Hg) ≤0.02
锑(Sb) ≤30.0
Lead (Pb) ≤ 0.2 ≤ 0.8
Arsenic (As) ≤ 0.2 ≤ 1.0
Nickel (Ni) ≤1.0 ≤4.0
Cobalt (Co) ≤ 1.0 ≤ 4.0
Extractable heavy metal/(mg/kg)
Copper (Cu) ≤ 25.0 ≤ 50.0
Pentachlorophenol (PCP) ≤0.05 ≤0.5 Chlorophenol/(mg/kg) Tetrachlorophenol (TeCP) ≤0.05 ≤0.5
O-phenylphenol (OPP)/(mg/kg) ≤ 0.5 ≤ 1.0
Dyes that can decompose carcinogenic aromatic amines (see Appendix A for types)/(mg/kg) ≤ 30.0
Odor/grade ≤ 3
6.2 Synthetic leather products meet the requirements of Table 1, while other hazardous substances limits should also meet the requirements of Table 2.
Table 2 Limits of other harmful substances in synthetic leather
Classification item
Class A, Class B, Class C
Volatile Organic Compounds (VOC)/(mg/kg) ≤ 100
Tributyltin (TBT) ≤0.5 ≤1.0
Dibutyltin (DBT) ≤1.0 ≤2.0 Organotin Compound/(mg/kg)
Monobutyltin (MBT) ≤1.0 ≤2.0
Chlorinated benzene and chlorinated toluene (see Appendix B for types)/(mg/kg) ≤ 1.0
6.3 The following substances shall not be used in the production of the product.
(1) Carcinogenic dyes (see Appendix C for types);
(2) Sensitizing dyes (see Appendix D for types);
(3) Blue dye (CI611-070-00-2);
(4) alkylphenol ethoxylates (APEO);
(5) short-chain chlorinated paraffin (C10-C13);
(6) Polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDE);
(7) polycyclic aromatic hydrocarbons (PAHs);
(8) Perfluorooctane sulfonate (PFOS);
(9) Dimethyl fumarate (DMFu).
6.4 The product shall be marked with a product category (such as Class A, Class B or Class C) that complies with this standard.
7 Inspection method
7.1 Technical content 6.1 The detection of pH and its dilution difference is carried out in accordance with the method specified in QB/T 2724-2005.
7.2 Technical content 6.1 The detection of free formaldehyde is carried out in accordance with the method specified in GB/T.19941-2005.
7.3 Technical content 6.1 The detection of hexavalent chromium in accordance with the method specified in GB/T 22807-2008.
7.4 Technical content The detection of other extractable heavy metals in 6.1 shall be carried out in accordance with the method specified in GB/T 22930-2008.
7.5 Technical content 6.1 The detection of chlorophenol in accordance with the method specified in GB/T 22808-2008.
7.6 Technical content 6.1 The detection of o-phenylphenol in accordance with the method specified in GB/T 20386-2006.
7.7 Technical content 6.1 The detection of dyes that can decompose carcinogenic aromatic amines is carried out in accordance with the method specified in GB/T.19942-2005.
7.8 Technical content 6.1 The detection of leather odor is carried out according to the method specified in QB/T 2725-2005.
The method specified in Appendix E is carried out.
7.9 The detection of volatile organic compounds (VOC) in Technical Content 6.2 is carried out in accordance with the method specified in Appendix F.
7.10 Technical content 6.2 The detection of organotin compounds shall be carried out in accordance with the method specified in GB/T 22932-2008.
7.11 Technical content 6.2 The detection of chlorinated benzene and chlorinated toluene shall be carried out in accordance with the method specified in GB/T 20384-2006.
7.12 Other indicators in the technical content are verified by means of document review combined with on-site inspection.
Appendix A
(normative appendix)
Aromatic amines that are not allowed to decompose from dyes under reducing conditions
Serial No. Chinese Name English Name Chemical Abstract Number (CAS No.)
1 4-aminobiphenyl 4-Aminodiphenyl 92-67-1
2 benzidine Benzidine 92-87-5
3 4-Chloro-o-toluidine 4-Chloro-o-toluidine 95-69-2
4 2-Naphthylamine 2-Naphthylamine 91-59-8
5 o-aminoazotoluene o-Amino-azotoluene 97-56-3
6 2-Amino-4-nitrotoluene 2-Amino-4-nitrotoluene 99-55-8
7 p-chloroaniline p-Chloroaniline 106-47-8
8 2,4-diaminoanisole 2,4-Diaminoanisole 615-05-4
9 4,4'-diaminodiphenylmethane 4,4'-Diaminodiphenylmethane 101-77-9
10 3,3'-Dichlorobenzidine 3,3'-Dichlorobenzidine 91-94-1
11 3,3'-dimethoxybenzidine 3,3'-Dimethoxybenzidine 119-90-4
12 3,3'-Dimethylbenzidine 3,3'-Dimethylbenzidine 119-93-7
13 3,3'-Dimethyl-4,4'-diaminodiphenylmethane 3,3'-Dimethyl-4,4'-diaminodipheylmethane 838-88-0
14 3-Amino-p-toluidine methyl p-Cresidine 120-71-8
15 4,4'-methine-bis-(2-chloroaniline) 4,4'-Methylene-bis-(2-chloroaniline) 101-14-4
16 4,4'-diaminodiphenyl ether 4,4'-Oxydianiline 101-80-4
17 4,4'-diaminodiphenyl sulfide 4,4'-Thiodianiline 139-65-1
18 o-toluidine (2-methylaniline) o-Toluidine 95-53-4
19 2,4-Diaminotoluene 2,4-Diaminotoluene 95-80-7
20 2,4,5-trimethylaniline 2,4,5-Trimethylaniline 137-17-7
21 o-methoxyaniline (o-aminoanisole) o-Anisidine 90-04-0
22 2,4-dimethylaniline 2,4-Xylidine 95-68-1
23 2,6-dimethylaniline 2,6-Xylidine 87-62-7
24 4-aminoazobenzene 4-Aminoazobenzene 60-09-3
Appendix B
(normative appendix)
Chlorinated benzene and toluene chloride
Chinese name English name Chinese name English name
Dichlorobenzene Dichlorobenzene Chlorotoluene Chlorotoluene
Trichlorobenzene Dichlorotoluene
Tetrachlorobenzene Trichlorotoluene
Pentachlorobenzene tetrachlorotoluene Tetrachlorotoluene
Hexachlorobenzene Hexachlorobenzene Pentachlorotoluene
Appendix C
(normative appendix)
Dyes recognized as carcinogenic
Chinese name English name CI index number CA login number
CI Acid Red 26 CIAcid Red 26 CI16150 3761-53-3
CI Basic Red 9 CIBasic Red 9 CI42500 25620-78-4
CI Basic Violet 14 CIBasic Violet 14 CI42510 632-99-5
CI Direct Black 38 CIDirect Black 38 CI30235 1937-37-7
CI Direct Blue 6 CIDirect Blue 6 CI22610 2602-46-2
CI Direct Red 28 CIDirect Red 28 CI22120 573-58-0
CI Disperse Blue 1 CIDisperse Blue 1 CI64500 2475-45-8
CI Disperse Orange 11 CIDisperse Orange 11 CI60700 82-28-0
CI Disperse Yellow 3 CIDisperse Yellow 3 CI11855 2832-40-8
Appendix D
(normative appendix)
Dyes recognized as sensitizing
Chinese name English name CI index number CA login number
CI Disperse Blue 1 CIDisperse Blue 1 CI64500 2475-45-8
CI Disperse Blue 3 CIDisperse Blue 3 CI61505 2475-46-9
CI Disperse Blue 7 CIDisperse Blue 7 CI62500 3179-90-6
CI Disperse Blue 26 CIDisperse Blue 26 CI63305
CI Disperse Blue 35 CIDisperse Blue 35 12222-75-2
CI Disperse Blue 102 CIDisperse Blue 102 12222-97-8
CI Disperse Blue 106 CIDisperse Blue 106 12222-01-7
CI Disperse Blue 124 CIDisperse Blue 124 61951-51-7
CI Disperse Brown 1 CIDisperse Brown 1 23355-64-8
CI Disperse Orange 1 CIDisperse Orange 1 CI11080 2581-69-3
CI Disperse Orange 3 CIDisperse Orange 3 CI64005 730-40-5
CI Disperse Orange 37/76 CIDisperse Orange 37/76
CI Disperse Red 1 CIDisperse Red 1 CI11110 2872-52-8
CI Disperse Red 11 CIDisperse Red 11 CI62015 2872-48-2
CI Disperse Red 17 CIDisperse Red 17 CI11210 3179-89-3
CI Disperse Yellow 1 CIDisperse Yellow 1 CI10345
CI Disperse Yellow 3 CIDisperse Yellow 3 CI11855 2832-40-3
CI Disperse Yellow 9 CIDisperse Yellow 9 CI10375 6373-73-5
CI Disperse Yellow 39 CIDisperse Yellow 39
CI Disperse Yellow 49 CIDisperse Yellow 49
Appendix E
(normative appendix)
Determination of odor of synthetic leather
E.1 Test equipment
E.1.1 Thermostatic test chamber with air circulation function, temperature deviation is ± 2 °C.
E.1.2 A 3 L glass container with an odorless seal and lid that should be cleaned and kept clean before any test.
Flavor status.
E.2 Sample preparation
Cut a (150 ± 5) cm3 synthetic leather sample, the size of which should be converted according to the thickness of the synthetic leather, such as a synthetic leather of 1.0 mm thickness.
The sample size is approximately 39 cm x 39 cm.
E.3 Tester
The tester should have no olfactory defects, and smokers, heavy-scented cosmetics, traditional spices or tobacco users are not suitable.
Tester.
E.4 Test procedure
Follow the steps below to perform the measurement.
E.4.1 Adjust the temperature of the incubator to (80 ± 2) °C.
E.4.2 Place the sample in a 3 L glass container, seal it and place it in an (80 ± 2) °C incubator for (120 ± 10) min;
E.4.3 Remove the container with the sample from the incubator and cool to (60 ± 5) °C for odor determination.
E.4.4 After being measured by 3 inspectors, return the container with the sample back to the (80 ± 2) °C incubator, and then other test personnel
The measurement is carried out in accordance with E.4.3.
E.4.5 At least 5 testers are required to participate in the determination and determine the level of odour according to Table E.1, if testing between testers
The result gap is more than two grades and should be re-measured.
E.4.6 The arithmetic mean of each scoring result is used to describe the odor characteristics. If the rating is between the two, the closest half is four.
Round off.
Table E.1 Odour level
Grade odor characteristics
Level 1 is not easy to feel
Level 2 can be felt, but not pungent
Level 3 can be noticeably felt, but not pungent
Level 4 pungent
Level 5 is very pungent
Level 6 is intolerable
Appendix F
(normative appendix)
Determination of volatile organic compounds (VOC) content
F.1 principle
In a constant temperature closed container, the volatile organic compounds in the sample are distributed between the gas and solid phases to achieve equilibrium, and the solid phase gas sample is taken.
The gas chromatograph (GC/MSD) with mass selective detector was used for the determination, confirmed by selective ion detection, and quantified by external standard method.
F.2 Instruments and reagents
The reagents used were of analytical grade unless otherwise stated.
F.2.1 Gas Chromatography-Mass Spectrometer
F.2.2 Automatic Headspace Sampler
F.2.3 Headspace sample bottle with Teflon-sealed silicone rubber mat
F.2.4 10 μl airtight syringe
F.2.5 Acetone
F.2.6 toluene
F.2.7 Correcting working solution
Toluene is prepared at a concentration of 0.5 mg/ml, 1.0 mg/ml, 5.0 mg/ml, 10.0 mg/ml, respectively, using acetone or other suitable solvent.
50.0 mg/ml toluene/acetone solution (freshly prepared).
F.3 Analysis steps
F.3.1 Sample preparation
The sample was tested after 7 days from the date of production.
Take a representative sample, cut it to 5 mm × 5 mm or less and mix. Weigh 2.00 g of the sample from the mixture to the nearest 0.01 g.
Place in the headspace sample bottle (F.2.3), cover with silicone rubber pad and aluminum cover, seal with sealing tool, put into the automatic headspace sampler to be tested
set.
F.3.2 Determination
Gas chromatography-mass spectrometry conditions.
Since the test results depend on the instrument used, it is not possible to give a universal parameter for chromatographic analysis. The following parameters have been proven
It is suitable for testing.
The headspace vial has a heating temperature of 120 ° C and a heating equilibration time of 45 min.
a) Column. HP-5 MS 30 m × 0.25 mm × 0.5 μm or equivalent;
b) Column temperature. 50 ° C (3 min) → 12/min.200 ° C ° C (4 min);
c) inlet temperature..200 ° C;
d) injection method. split ratio 1.20;
e) carrier gas. helium, purity ≥ 99.999%, 1.0 ml/min;
f) chromatography-mass spectrometry interface temperature. 250 ° C;
g) Ionization mode. EI.
F.3.3 Calculation of results
F.3.3.1 Determination of correction factor
4 μl ± 0.04 μl calibration working solution (F.2.7), 10 μl micro-injector into 5 headspace sample bottles, quickly seal
The mouth tool is sealed and placed in an automatic headspace sampler (F.2.2). After heating at 120 °C for 5 min, it is analyzed by gas chromatography-mass spectrometry.
The correction factor (KG) was determined using the peak area and the corresponding concentration.
F.3.3.2 Volatile organic compounds
The correction factor corrected by the total peak area and acetone is calculated according to formula (1).
AA
K m
Σ −= ×× (1)
Where. EG - the content of volatile organic compounds in the sample, mg/kg;
∑A--the total chromatographic peak area in the sample;
A0--blank chromatographic peak area;
KG--correction factor;
M--the mass of the sample, g;
V--the injection volume of the standard solution, ml.
Note. When taking 2 g sample, the volume is 20 ml of the headspace bottle, V is 4 μl; when taking 1 g sample, the volume is 10 ml of the headspace bottle, V is 2 μl, according to this
analogy.
F.3.3.3 Volatile amount of individual substances
Calculated according to formula (2).
A CE
A m
V×= ×× (2)
Where. Ei--the amount of volatilization of a substance in the sample, mg/kg;
A--the peak area of a substance in the sample;
As--the peak area of a single substance in the standard working fluid;
C--the mass concentration of a single substance in the standard working fluid, mg/L;
M--the mass of the sample, g;
V--the injection volume of the standard solution, ml.
F.4 Determination of low limits, recovery and precision
F.4.1 Determination of the lower limit. The lower limit of this method is 0.5 mg/kg.
F.4.2 Recovery rate. When adding 0.5-50 mg/kg benzene series to the sample, the recovery rate is 88.0%-96.1%.
F.4.3 Precision
In the same laboratory, the same equipment is used by the same operator, according to the same test method, and the same object is measured in a short time.
The absolute difference between the two independent test results obtained by the tests independently of each other is not more than 10% of the arithmetic mean of the two measured values.
The case where it is greater than 10% of the arithmetic mean of these two measured values does not exceed 5%.
F.5 Test report
The test report should at least give the following.
a) sample description;
b) the standard used;
c) test results;
d) deviation from the standard;
e) Test date.
2.359
3.659
3.891 4.598
5.752
5.958
6.607
6.551
11.467
3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00
time
14.304
Figure F.1 Organic volatile GC/MS total ion chromatogram
Table F.1 GC/MS characteristic ions of organic volatile names and their standards
Characteristic ion /u No. Name retention time/min Chemical Abstract No. (CAS No.) Qualitative quantification
1 benzene 2.359 71-43-2 78,74 78
2 toluene 3.659 108-88-3 91,65,51 91
3 N,N-dimethylformamide 3.891 627-45-2 44,58,73 73
4 butyl acetate 4.598 123-86-4 87,43,56 87
5 ethylbenzene 5.752 100-41-4 106,91 106
6 p-xylene 5.958 106-42-3 106,91 106
7 styrene 6.551 100-42-5 104,78,51 104
8 o-xylene 6.607 95-47-6 106,91 106
9 n-undecane 11.467 1120-21-4 156,57,43 156
10 n-tetradecane 14.304 629-59-4 198,57,43 198
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