Translated English of Chinese Standard: GB18581-2009 www.chinesestandard.net Sales@ChineseStandard.net GB NATIONAL STANDARD OF THE PEOPLE S REPUBLIC OF CHINA ICS 87.040 G 51 GB 18581-2009 Replacing GB 18581-2001 Indoor decorating and refurbishing materials - Limit of harmful substances of solvent based coatings for woodenware 室内装饰装修材料 溶剂型木器涂料中有害物质限量 Issued on: September 30, 2009 Implemented on: June 01, 2010 Issued by: General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China; Standardization Administration of the People's Republic of China. www.chinesestandard.net Page 1 of 26
Table of contents Foreword... 3 1 Scope... 5 2 Normative references... 5 3 Terms and definitions... 6 4 Requirements... 7 5 Test method... 8 6 Inspection rules... 8 7 Packaging mark... 9 8 Painting safety and protection... 9 Appendix A (Normative) Determination of volatile organic compounds (VOC) content... 10 Appendix B (Normative) Determination of benzene, toluene, ethylbenzene, xylene and methanol content... 17 Appendix C (Normative) Determination of halogenated hydrocarbon content 22 www.chinesestandard.net Page 2 of 26
Foreword All the technical contents of this standard are mandatory. The standard replaces GB 18581-2001 Indoor decorating and refurbishing materials - Limit of harmful substances of solvent based coatings for woodenware. As compared with GB 18581-2001, main technical changes of this standard are as follows: - DEFINE the scope of application as the polyurethane, nitro and alkyd solvent based coatings (including primer and finish) for woodware AND the solvent based putty for woodware for the purposes of indoor decorating & refurbishing and factory coating; - In the scope of application, ADD the solvent based putty for woodware; and SPECIFY the limit of harmful substance; - In the scope of application, SPECIFY clearly that it is not applicable to the radiation curing coatings and unsaturated polyester putty; - In the nitro-based paint, ADD the methanol content control items; - DEFINE the total content control item of toluene and xylene as the total content control item of toluene, ethylbenzene and xylene; - CHANGE the original standard free toluene diisocyanate (TDI) content control item to free diisocyanate (TDI, HDI) total content control item; - ADD the halogenated hydrocarbon content control item; - MAKE the limits of the total content of volatile organic compounds, free diisocyanate (TDI, HDI) total content, total content of toluene, ethylbenzene and xylene, and the benzene content in the coating more stringent. - ADD the definition of volatile organic compounds and volatile organic compounds content; ESTABLISH the corresponding test methods; - ESTABLISH the test methods of methanol and halogenated hydrocarbon content; - MODIFY and IMPROVE the benzene, toluene, ethylbenzene and xylene content test method; www.chinesestandard.net Page 3 of 26
Indoor decorating and refurbishing materials - Limit of harmful substances of solvent based coatings for woodenware 1 Scope This standard specifies the allowable limit value requirements, test methods, inspection rules, packaging marks, coating safety and protection, etc., of the human and environmental harmful substances in polyurethane, nitro and alkyd solvent based coatings of woodware AND the solvent based putty of woodware for indoor decorating and refurbishing purposes. This standard applies to the polyurethane, nitro and alkyd solvent based coatings (including primer and finish) for woodware AND the solvent based putty for woodware for the purposes of indoor decorating & refurbishing and factory coating. It does not apply to radiation curing coatings and unsaturated polyester putty. 2 Normative references The provisions in following documents become the provisions of this Standard through reference in this Standard. For the dated references, the subsequent amendments (excluding corrections) or revisions do not apply to this Standard; however, parties who reach an agreement based on this Standard are encouraged to study if the latest versions of these documents are applicable. For undated references, the latest edition of the referenced document applies. GB/T 1250 Method of expression and determination of limit value GB/T 1725-2007 Paints varnishes and plastics - Determination of non-volatile-matter content (ISO 3251:2003, IDT) GB/T 3186 Paint, varnishes and raw materials for paints and varnishes - Sampling (GB/T 3186-2006, ISO 15528:2000, IDT) GB/T 6750-2007 Paints and varnishes - Determination of density - Pyknometer method (ISO 2811-1:1997, Paints and varnishes - Determination of density - Part 1: Pyknometer method, IDT) www.chinesestandard.net Page 5 of 26
GB/T 9750 Marks for package of coating products GB/T 9754-2007 Paints and varnishes - Determination of specular gloss of non-metallic paint films at 20, 60 and 85 (ISO 2813:1994, IDT) GB/T 18446-2009 Binders for paints and varnishes - Determination of monomeric diisocyanates in isocyanate resins (ISO 10283:2007, IDT) GB 18582-2008 Indoor decorating and refurbishing materials - Limit of harmful substances of interior architectural coatings 3 Terms and definitions The following terms and definitions apply to this standard. 3.1 3.2 3.3 3.4 3.5 Volatile organic compounds (VOC) It refers to, at the standard atmospheric pressure of 101.3 kpa, any organic compound having an initial boiling point of less than or equal to 250 C. Volatile organic compounds content It refers to the content of the volatile organic compounds as obtained through testing the product by the specified test methods. Polyurethane coatings It refers to a kind of coating for which the main film forming substance is the polyamine (methacrylic acid) ester resin which is formed by the reaction of polyisocyanate and an active hydrogen-containing compound. Nitrocellulose coatings It refers to a kind of coating for which the main film forming substance is the nitric acid cellulose which is formed by the esterification reaction between the mixture of nitric acid and sulfuric acid and cellulose. www.chinesestandard.net Page 6 of 26
- In case of major change in the production formula, process, the key source of raw materials and product construction proportioning; - In case of production restoration after suspension for three months. 6.2 Determination of test results 6.2.1 The test results shall be determined in accordance with the rounding off value comparison method in GB/T 1250. When the test result after rounding off is 0, 0.0, the result is reported as one significant digit. 6.2.2 While reporting the inspection results, it shall indicate at the same time the stated construction proportioning of the product. 6.2.3 When the test results of all the items reach to the requirements of this standard, the products comply with the requirements of this standard. 7 Packaging mark 7.1 The product packaging mark may, in addition to comply with the provisions of GB/T 9750, be indicated accordingly if passing the inspection in accordance with this standard. 7.2 As for the coating and putty composed of double components or multiple components, it shall clarify the construction proportioning of each component on the packing mark or product instruction manual. As for the coating and putty requiring dilution before use, it shall clarify the dilution proportion in the packing mark or the product instruction manual. 8 Painting safety and protection 8.1 The room shall be well ventilated during painting. 8.2 The construction workers shall wear the necessary protective equipment during coating. 8.3 After completion of coating, it shall continuously maintain the indoor air circulation. www.chinesestandard.net Page 9 of 26
Split ratio: split sample injection, with the split ratio adjustable; Injection volume: 1.0 μl. Note: It may also select the optimal gas chromatographic test conditions in accordance with the performance of the instrument used and the actual conditions of the sample to be tested. A.5 Test procedures All tests shall be subjected to secondary parallel determination. A.5.1 Density PREPARE the mixed sample in accordance with the stated construction proportioning of the product; after stirring it uniformly, DETERMINE the sample density in accordance with the provisions of GB/T 6750-2007, at the test temperature of (23 ± 2) C. A.5.2 Volatile content PREPARE the mixed sample in accordance with the stated construction proportioning of the product; after stirring it uniformly, DETERMINE the content of the non-volatile compound of the sample in accordance with the provisions of GB/T 1725-2007, in grams per gram (g/g); USE 1 to minus the content of the non-volatile compound to obtain the content of the volatile compound, in grams per gram (g/g). WEIGH the sample amount (1 ± 0.1) g, AND the test conditions: (105 ± 2) C/h. A.5.3 Gloss The polyurethane coating film gloss is determined in accordance with the provisions of GB/T 9754-2007. PREPARE the mixed sample in accordance with the stated construction proportioning of the product; after stirring it uniformly, USE the wet film preparer with the groove depth of (100 ± 2) μm to prepare sample on a flat glass. As for varnish, it shall use the black glass or the flat glass back coated with matt black paint as the substrate. DRY the sample plate for 48 h under the conditions of (23 ± 2) C and a relative humidity of (50 ± 5)%; USE the 60 specular gloss meter to test it. A.5.4 Volatile organic compounds (VOC) content A.5.4.1 Determination of the VOC content containing no organic compounds with a boiling point greater than 250 C www.chinesestandard.net Page 12 of 26
FT-IR spectrometer (A.3.1.3.3), under the gas chromatograph test conditions as specified in A.4. Note: As for the prepared mixed sample of the polyurethane coatings, it shall make the test as soon as possible. A.5.4.2.3 Calibration A.5.4.2.3.1 If the compounds used in the calibration are commercially available, it shall use the following methods to determine the relative correction factor. A.5.4.2.3.1.1 Preparation of calibration samples: Respectively WEIGH a certain amount (accurate to 0.1 mg) of calibration compounds (A.2.6) as authenticated in accordance with A.5.4.2.2 into the vial (A.3.3), AND the weighing mass shall be at the same order of magnitude with the content of each compound in the tested sample. WEIGH the internal standard substance (A.2.5) at the same order of magnitude with the tested chemical compound into the same vial; USE an appropriate amount of diluent (A.2.7) to dilute the mixture; SEAL the vial and SHAKE it uniformly. A.5.4.2.3.1.2 Test of relative correction factor: Under the gas chromatograph conditions same as the tested sample, OPTIMIZE the instrument parameters in accordance with the provisions of A.5.4.2.1. INJECT an appropriate amount of calibrated mixture into the gas chromatograph; RECORD the chromatogram; FOLLOW the equation (A.2) to calculate respectively the relative correction factor of each chemical compound: Where: Ri - The relative correction factor of compound i; mci - The mass of compound i in the calibration mixture, in grams (g); mis - The mass of internal standard substance in the calibration mixture, in grams (g); Ais - The peak area of the internal standard substance; Aci - The peak area of compound i. The result of the determination retains three significant digits. www.chinesestandard.net Page 14 of 26
Appendix B (Normative) Determination of benzene, toluene, ethylbenzene, xylene and methanol content B.1 Principle The sample is, after dilution, directly injected into the gas chromatograph, separated by the column, detected by hydrogen flame ionization detector, AND quantified by internal standard method. B.2 Materials and reagents B.2.1 Carrier gas: nitrogen, purity 99.995%. B.2.2 Fuel gas: hydrogen, purity 99.995%. B.2.3 Oxidant gas: air. B.2.4 Supporting gas (pad purging and make-up gas): nitrogen gas of the same nature as carrier gas. B.2.5 Internal standard substance: a compound that does not exist in the sample AND this compound is completely separable from the other components on the chromatogram, with a purity of at least 99% (mass fraction) or known purity, such as n-heptane and n-pentane, etc. B.2.6 Calibration compounds: benzene, toluene, ethylbenzene, xylene and methanol, purity of at least 99% (mass fraction) or known purity. B.2.7 Dilution solvent: An organic solvent used to dilute the sample, containing no other substances which may interfere with the test, with a purity of at least 99% (mass fraction) or known purity, for example: ethyl acetate, n-hexane and so on. B.3 Instruments and equipment B.3.1 Gas chromatograph, with the following configurations: B.3.1.1 Inlet of the split device, AND the vaporization chamber liner can be replaced. www.chinesestandard.net Page 17 of 26
The injection volume shall match with split ratio, in order to avoid exceeding the column capacity; AND it shall be within the linear range of the instrument detector. B.5.2 Qualitative analysis B.5.2.1 In accordance with the provisions of B.5.1, OPTIMIZE the instrument parameters. B.5.2.2 Determination of retention time of the tested compound INJECT 1.0 μl of the standard mixed solution containing the tested compound as specified in B.2.6 into the chromatograph; RECORD the retention time of each tested compound. B.5.2.3 Qualitative analysis PREPARE the mixed sample in accordance with the stated construction proportioning of the product; after stirring it uniformly, WEIGH about 2 g of sample; USE an appropriate amount of diluent (B.2.7) to dilute the sample; USE the sample injector (B.3.2) to take 1.0 μl of the uniformly mixed sample to inject it into the chromatograph; RECORD the chromatogram; COMPARE it with the retention time of the tested standard compound which had been subjected to the determination of B.5.2.2 to determine whether there is the tested compounds. Note: As for the prepared mixed sample of the polyurethane coatings, it shall make the test as soon as possible. B.5.3 Calibration B.5.3.1 Preparation of calibration samples: Respectively WEIGH a certain amount (accurate to 0.1 mg) of calibration compounds in B.2.6 into the vial (B.3.3), AND the weighing mass shall be at the same order of magnitude with the content of each compound in the tested sample. WEIGH the internal standard substance (B.2.5) at the same order of magnitude with the tested chemical compound into the same vial; USE an appropriate amount of diluent (B.2.7) to dilute the mixture; SEAL the vial and SHAKE it uniformly. B.5.3.2 Test of relative correction factor: Under the gas chromatograph conditions same as the tested sample, OPTIMIZE the instrument parameters in accordance with the provisions of B.5.1. INJECT an appropriate amount of calibrated mixture into the gas chromatograph; RECORD the chromatogram; FOLLOW the equation (B.1) to calculate respectively the relative correction factor of each chemical compound: www.chinesestandard.net Page 19 of 26
Appendix C (Normative) Determination of halogenated hydrocarbon content C.1 Principle The sample is, after being diluted, directly injected into the gas chromatograph. The dichloromethane, dichloroethane, trichloromethane, trichloroethane and carbon tetrachloride are completely separated from the other components by capillary column, analyzed by electron capture detector, AND subjected to quantitation by the internal standard method. C.2 Materials and reagents C.2.1 Carrier gas: nitrogen, purity 99.995%. C.2.2 Supporting gas (pad purging and make-up gas): nitrogen gas of the same nature as carrier gas. C.2.3 Internal standard substance: a compound that does not exist in the sample AND this compound is completely separable from the other components on the chromatogram, with a purity of at least 99% (mass fraction) or known purity, such as bromopropane and the like. C.2.4 Calibration compounds: dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloromethane, 1,1,1-trichloroethane, 1,1,2- trichloroethane, and carbon tetrachloride, having a purity of at least 99% (mass fraction) or known purity. C.2.5 Dilution solvent: An organic solvent used to dilute the sample, containing on other substances which may interfere with the test, with a purity of at least 99% (mass fraction) or known purity, for example: ethyl acetate, n-hexane and so on. C.3 Instruments and equipment C.3.1 Gas chromatograph, with the following configurations: C.3.1.1 Inlet of the split device, AND the vaporization chamber liner can be replaced. www.chinesestandard.net Page 22 of 26
The injection volume shall match with split ratio, in order to avoid exceeding the column capacity; AND it shall be within the linear range of the instrument detector. C.5.2 Qualitative analysis C.5.2.1 In accordance with the provisions of C.5.1, OPTIMIZE the instrument parameters. C.5.2.2 Determination of retention time of the tested compound INJECT 0.2 μl of the standard mixed solution containing the tested compound as specified in C.2.4 into the chromatograph; RECORD the retention time of each tested compound. C.5.2.3 Qualitative analysis PREPARE the mixed sample in accordance with the stated construction proportioning of the product; after stirring it uniformly, WEIGH about 2 g of sample; USE an appropriate amount of diluent (C.2.5) to dilute the sample; USE the sample injector (C.3.2) to take 0.2 μl of the uniformly mixed sample to inject it into the chromatograph; RECORD the chromatogram; COMPARE it with the retention time of the tested standard compound which had been subjected to the determination of C.5.2.2 to determine whether there is the tested compounds. Note: As for the prepared mixed sample of the polyurethane coatings, it shall make the test as soon as possible. C.5.3 Calibration C.5.3.1 Preparation of calibration samples: Respectively WEIGH a certain amount (accurate to 0.1 mg) of calibration compounds in C.2.4 into the vial (C.3.3), AND the weighing mass shall be at the same order of magnitude with the content of each compound in the tested sample. WEIGH the internal standard substance (C.2.3) at the same order of magnitude with the tested chemical compound into the same vial; USE an appropriate amount of diluent (C.2.5) to dilute the mixture (the dilution concentration shall be within the linear range of the instrument detector; otherwise it shall increase the dilution factor or use multiple dilution in stages); SEAL the vial and SHAKE it uniformly. C.5.3.2 Determination of relative correction factor Under the gas chromatograph conditions same as the tested sample, OPTIMIZE the instrument parameters in accordance with the provisions of C.5.1. INJECT an appropriate amount of calibrated mixture into the gas www.chinesestandard.net Page 24 of 26