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This standard is developed in accordance with the rules given in GB/T 1.1-2009.
This standard was proposed by China Petroleum and Chemical Industry Federation.
This standard is under the jurisdiction of National Technical Committee 5 on Paints & Pigments of Standardization Administration of China (SAC/TC 5).
Introduction
This standard has been formulated in order to implement the relevant requirements of Law of the People's Republic of China on the prevention and control of atmospheric pollution, Comprehensive work plan for energy conservation and emission reduction in the 13th Five-Year Plan period, Work programme for prevention and control of volatile organic compound pollution in the 13th Five-Year Plan period, and Notice of the State Council on printing and distributing the Three-Year Action Plan to win the battle of safeguarding blue sky. This standard has been prepared according to the principles as follows:
a) Well-developed standards and norms at home and abroad are actively consulted to embody the principle of “scientificity, progressiveness, feasibility and normalization”.
b) Following the principle of coordination with mandatory national standards, keeping basically consistent with mandatory national standards in classification, and providing higher technical requirements than the relevant technical requirements of mandatory national standards.
c) The requirements of environmental protection and the needs of industry development are comprehensively considered so as to achieve technological progressiveness and economical rationality.
In recent years, environmentally friendly coatings, such as water-borne coatings, high-solid coatings, solvent-free coatings, radiation-curable coatings, powder coatings, etc., have made considerable progress under the guidance of environmental protection requirements and industrial policies. For example, water-borne coating varieties such as architectural wall coating, container coating and automotive OEM coating have been successfully developed and widely used. Although powder coatings, solvent-free coatings and radiation-curable coatings are limited by application method, their application scope is still gradually expanding. The technology and application of high solid coating are becoming more and more mature. All these have strongly promoted the green transformation of China's coating industry to coatings with low volatile organic compound content.
Coatings are widely used, and the technological development and user requirements of coating products vary considerably with type and application. Therefore, the concept of low volatile organic compound (VOC) content mainly refers to a relative reduction of VOC content at the current state of art so as to reduce VOCs from the source.
VOC emission of coating product is not only related to the VOC in the container of coating product and the VOC in the coating, but also related to the coating maintenance frequency after application. Coatings with good quality and durability have long maintenance intervals and less VOC emission in their service life cycle.
This standard is not intended for the selection of coatings with low volatile organic compound content. Each category of coating has its specific application requirements.
This standard specifies requirements, test methods, judgment rules, package marking and implementation of standard for coating products with low volatile organic compound content.
This standard is applicable to the determination of coating products with low volatile organic compound content.
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 1725-2007 Paints, varnishes and plastics—Determination of non-volatile-matter content
GB/T 3186 Paints, varnishes and raw materials for paints and varnishes—Sampling
GB/T 5206-2015 Paints and varnishes—Terms and definitions
GB/T 6682-2008 Water for analytical laboratory use—Specification and test methods
GB/T 6750-2007 Paints and varnishes—Determination of density—Pyknometer method
GB/T 8170-2008 Rules of rounding off for numerical values & expression and judgment of limiting values
GB/T 9750 Marks for package of coating products
GB/T 23985-2009 Paints and varnishes—Determination of volatile organic compound (VOC) content—Difference method
GB/T 23986-2009 Paints and varnishes—Determination of volatile organic compound (VOC) content—Gas-chromatographic method
GB/T 34675-2017 Determination of volatile organic compound (VOC) content in radiation curable coatings
GB/T 34682-2017 Determination of volatile organic compound (VOC) content in reactive diluent containing coatings
3 Terms and definitions
For the purposes of this document, the terms and definitions given in GB/T 5206-2015 and the following apply. For the convenience of use, some terms and definitions in GB/T 5206-2015 are listed below.
coating product, in which the mass of volatile organic compounds in as applied condition meets the requirements to the content limit of volatile organic compounds for corresponding products given in this standard
3.2
coating material
liquid, pasty or powdered product, which, as applied onto the substrate, can form a coating with protection, decoration and/or other special functions
[GB/T 5206-2015, Definition 2.51]
3.3
volatile organic compound (VOC)
an organic compound that participates in atmospheric photochemical reactions, or is defined in accordance with relevant provisions
3.4
volatile organic compound content
VOC content
mass of VOCs in coatings measured under prescribed conditions
[GB/T 5206-2015, Definition 2.271]
3.5
application condition
the condition under which the application of the mixture of all the product components is allowed once the application method and application conditions meet the requirements in the technical specifications of the product
4 Requirements
The limits of VOC content in water-borne coating, solvent-based coating, solvent-free coating and radiation curable coating shall meet the requirements of Tables 1, 2, 3 and 4 respectively.
For water-borne coatings and water-borne radiation curable coatings, the dilution ratio with water is not considered. Other category of coating shall be determined after mixing according to the application ratio in the application condition as stated for the product. Where the consumption of one of the components is within a certain range, determination shall be carried out after mixing according to the maximum ratio specified for the application ratio of the product under application condition. Where the coating product is suitable for multiple applications, the strictest limit value shall apply.
Foreword i Introduction ii 1 Scope 2 Normative references 3 Terms and definitions 4 Requirements 5 Test methods 6 Judgment rules 7 Package marking 8 Standard implementation Annex A (Normative) Determination of moisture content—Gas chromatographic method Bibliography
5测试方法 5.1 取样 产品按GB/T 3186的规定取样，也可按商定方法取样。取样量根据检验需要确定。 5.2试验方法 5.2.1 施工状态判定 按产品明示的施工状态下的施工配比混合后，再按产品规定的施工工艺进行施涂，如施涂无障碍，干膜厚度能控制在产品规定的范围内，涂膜外观符合产品明示的质量标准规定的要求，则判定为“与实际施工状态相符”。 注：如实验室无法模拟施工工艺，可在实际涂装现场进行确认与取样。 5.2.2 VOC含量 5.2.2.1 密度 按GB/T 6750—2007的规定进行，试验温度为(23±0.5)℃。 5.2.2.2水性涂料中VOC含量 5.2.2.2.1 建筑用墙面涂料、木器涂料、地坪涂料、防水涂料、道路标志标线涂料中VOC含量按GB/T 23986—2009的规定进行。色谱柱采用中等极性色谱柱(6％氰丙苯基/94％聚二甲基硅氧烷毛细管柱)，标记物为己二酸二乙酯。称取试样约1 g。水分含量的测定，按附录A的规定进行。VOC含量按GB/T 23986—2009中10.4计算。 5.2.2.2.2其他水性涂料中VOC含量 先按附录A的规定，测定水性涂料中水分含量。 如涂料中水分含量大于或等于70％(质量分数)，按GB/T 23986—2009的规定进行。色谱柱采用中等极性色谱柱(6％氰丙苯基/94％聚二甲基硅氧烷毛细管柱)，标记物为己二酸二乙酯。称取试样约1 g。VOC含量按GB/T 23986—2009中10.4计算。 如涂料中水分含量小于70％(质量分数)，按GB/T 23985—2009的规定进行。不挥发物含量按GB/T 1725—2007的规定进行，称取试样约1 g，在(105±2)℃条件下烘烤1 h。VOC含量按GB/T 23985—2009中8.4计算。 5.2.2.3 溶剂型涂料中VOC含量 不含活性稀释剂和水的溶剂型涂料按GB/T 23985—2009的规定进行。不挥发物含量按GB/T 1725—2007的规定进行，称取试样约1 g，在(105±2)℃条件下烘烤1 h。不测水分，水分含量设为零。不含活性稀释剂和水的溶剂型涂料中VOC含量的计算，按GB/T 23985—2009中8.3进行。 含活性稀释剂的溶剂型涂料按5.2.2.4的规定进行。 有意添加水的溶剂型涂料按GB/T 23985—2009的规定进行。不挥发物含量按GB/T 1725—2007的规定进行，称取试样约1 g，在(105±2)℃条件下烘烤1 h；水分含量的测定，按附录A的规定进行。VOC含量的计算，按GB/T 23985—2009中8.4进行。 5.2.2.4 无溶剂涂料中VOC含量 按GB/T 34682—2017的规定进行。不挥发物含量测定时的放置时间为标准试验环境[温度(23±2)℃；相对湿度(50±5)％]下放置24 h，或按产品说明书要求时间放置，但放置时间不大于7 d。不测水分，水分含量设为零。 VOC含量的计算，按GB/T 34682—2017中8.3进行。 5.2.2.5辐射固化涂料中VOC含量 按GB/T 34675—2017的规定进行。 水性辐射固化涂料中VOC含量的计算，按GB/T 34675—2017中8.4进行，水分含量的测定，按附录A的规定进行。 非水性辐射固化涂料中VOC含量的计算，按GB/T 34675—2017中8.3进行，不测水分，水分含量设为零。 6判定规则 6.1 检验结果判定，按GB/T 8170—2008中修约值比较法进行。 6.2 在检验报告中标明施工状态下VOC含量时，按5.2.1的规定进行施工状态判定。 6.3 施工状态判定和VOC含量均达到本标准的要求时，产品为符合本标准的要求。 7 包装标志 7.1 产品包装标志除应符合GB/T 9750的规定外，按本标准检验合格的产品可在包装标志上明示。 7.2包装标志上或产品说明书中应明确施工状态下的施工配比。 7.3包装标志上或产品说明书中应标明符合本标准的分类、产品类别和产品类型(或施涂方式)。 7.4含有活性稀释剂的溶剂型涂料应在包装标志上或产品说明书中明示。 7.5有意添加水的溶剂型涂料应在包装标志上或产品说明书中明示。 7.6 对于聚氨酯类、环氧类等多组分固化的涂料应在包装标志上或产品说明书中标明适用期。 8标准的实施 8.1 粉末涂料、无机建筑涂料(含建筑无机粉体涂装材料)、建筑用有机粉体涂料产品中VOC含量通常很少，属于低挥发性有机化合物含量涂料产品。 8.2涂装现场对施工状态下的涂料产品抽查时，对于多组分固化的涂料品种抽样检验，应在产品适用期内进行检验。 附 录 A (规范性附录) 水分含量的测定气相色谱法 A.1试剂和材料 A.1.1蒸馏水：符合GB/T 6682—2008中三级水的要求。 A.1.2稀释溶剂：用于稀释试样的并经分子筛干燥的有机溶剂，不含有任何干扰测试的物质。纯度至少为99％(质量分数)，或已知纯度。例如：二甲基甲酰胺等。 A.1.3 内标物：试样中不存在的并经分子筛干燥的化合物，且该化合物能够与色谱图上其他成分完全分离。纯度至少为99％(质量分数)，或已知纯度。例如：异丙醇等。 A.1.4分子筛：孔径为2 A～3 A，粒径为1.7 mm～5.0 mm。分子筛应再生后使用。 A.1.5载气：氢气或氦气，纯度≥99.995％。 A.2仪器设备 A.2.1 气相色谱仪：配有热导检测器及程序升温控制器。 A.2.2色谱柱：苯乙烯二乙烯基苯多孔聚合物的毛细管柱。 注：其他满足检验要求的色谱柱也可使用。 A.2.3进样器：微量注射器，10 μL。 A.2.4配样瓶：约10 mL的玻璃瓶，具有可密封的瓶盖。 A.2.5天平：实际分度值d＝0.1 mg。 A.3气相色谱测试条件 A.3.1 色谱柱：苯乙烯-二乙烯基苯多孔聚合物的毛细管柱，25 m×0.53 mm×10 μm。 A.3.2进样口温度：250℃。 A.3.3检测器温度：300℃。 A.3.4分流比：5：1。 A.3.5柱温：程序升温，100℃保持2 min，然后以20℃/min升至130℃并保持3 min；再以30℃/min升至200℃保持5 min。 A.3.6载气：氢气，流速6.5 mL/min。 注：也可根据所用气相色谱仪的性能、色谱柱类型及待测试样的实际情况选择最佳的气相色谱测试条件。 A.4测试步骤 A.4.1 测试水的相对响应因子R 在同一配样瓶(A.2.4)中称取约0.2 g的蒸馏水(A.1.1)和约0.2 g的内标物(A.1.3)，精确至0.1 mg，记录水的质量mw和内标物的质量mi，再加入5 mL稀释溶剂(A.1.2)，密封配样瓶(A.2.4)并摇匀。用微量注射器(A.2.3)吸取配样瓶(A.2.4)中的1 μL混合液注入色谱仪中，记录色谱图。按式(A.1)计算水的相对响应因子R： (A.1) 式中： R——水的相对响应因子； mi——内标物的质量，单位为克(g)； Aw——水的峰面积； mw——水的质量，单位为克(g)； Ai——内标物的峰面积。 若内标物和稀释溶剂不是无水试剂，则以同样量的内标物和稀释溶剂(混合液)，但不加水作为空白样，记录空白样中水的峰面积A0。按式(A.2)计算水的相对响应因子R： (A.2) 式中： R——水的相对响应因子； mi——内标物的质量，单位为克(g)； Aw——水的峰面积； A0——空白样中水的峰面积； mw——水的质量，单位为克(g)； Ai——内标物的峰面积。 平行测试两次，取两次测试结果的平均值，其相对偏差应小于5％。 A.4.2样品分析 称取搅拌均匀后的试样约0.6 g以及与水含量近似相等的内标物(A.1.3)于配样瓶(A.2.4)中，精确至0.1 mg，记录试样的质量ms和内标物的质量mi，再加入5 mL稀释溶剂(A.1.2)(稀释溶剂体积可根据样品状态调整)，密封配样瓶(A.2.4)并摇匀。同时准备一个不加试样的内标物和稀释溶剂混合液作为空白样。用力摇动或超声装有试样的配样瓶(A.2.4)15 min，放置5 min，使其沉淀[为使试样尽快沉淀，可在装有试样的配样瓶(A.2.4)内加入几粒小玻璃珠，然后用力摇动；也可使用低速离心机使其沉淀]。用微量注射器(A.2.3)吸取配样瓶(A.2.4)中的1 μL上层清液，注入色谱仪中，记录色谱图。 A.4.3计算 按式(A.3)计算试样中的水分含量ww： (A.3) 式中： ww——试样中的水分含量，以质量分数计； mi——内标物的质量，单位为克(g)； Aw——试样中水的峰面积； A0——空白样中水的峰面积； ms——试样的质量，单位为克(g)； Ai——内标物的峰面积； R——水的相对响应因子。 平行测试两次，取两次测试结果的平均值，保留至小数点后两位。 A.5精密度 A.5.1 重复性：水分含量大于或等于15％，同一操作者两次测试结果的相对偏差小于1.6％。 A.5.2 再现性：水分含量大于或等于15％，不同实验室间测试结果的相对偏差小于5％。 参考文献 [1] GB/T 2705—2003涂料产品分类和命名 [2] GB/T 33761—2017 绿色产品评价通则 [3] GB/T 35602—2017 绿色产品评价 涂料 [4] GB/T 35609—2017 绿色产品评价 防水与密封材料 [5] GB 37822—2019 挥发性有机物无组织排放控制标准 [6] GB 37824—2019涂料、油墨及胶粘剂工业大气污染物排放标准 [7] HG/T 4570—2013 汽车用水性涂料 [8] HG/T 5367.1—2018 轨道交通车辆用涂料 第1部分：水性涂料 [9] HJ 2537—2014环境标志产品技术要求 水性涂料 [10] ASTM D3960-05 (2018) Standard Practice for Determining Volatile Organic Compound (VOC)Content of Paints and Related Coatings [11] Basic Criteria for Award of The Blue Angel Environmental Label RAL-UZ 12a Low-Emis sion and Low-Pollutant Paints and Varnishes(Edition August 2011) [12] Commission Decision (EU) 2015/886 Amending Decision 2014/312/EU establishing the ecological criteria for the award of the EU Ecolabel for indoor and outdoor paints and varnishes [13] Commission Decision (EU) 2014/312 Establishing the ecological criteria for the award of the EU Ecolabel for indoor and outdoor paints and varnishes [14] Directive 2010/75/EU of the European Parliament and of the Council of 24 November 2010 on industrial emissions (integrated pollution prevention and control) [15] Directive 2004/42/CE of the European Parliament and of the Council of 21 April 2004 on the limitation of emissions of volatile organic compounds due to the use of organic solvents in certain paints and varnishes and vehicle refinishing products and amending Directive 1999/13/EC [16] EPA method 24 Determination Of Volatile Matter Content,Water Content, Density, Vol umeSolids, And Weight Solids Of Surface Coatings [17] Good Environmental Choice Australia Environmental Performance Standard Paints and Coatings (PCv2.2ii-2012) [18] GS-11 Green Seal Standard For Paints Coatings Stains and Sealers( Edition 3.2) [19] Hong Kong Green Label Scheme Product Environmental Criteria for Paint (GL-008-010) [20] Japan Eco mark Product Category No.126 "Paints"(Version 2.5) [21] Korea Eco-label Standards EL241:2014 Paints [22] Nordic Ecolabelling of Chemical building products (Version 2.7) [23] US 40 CFR Part 60—STANDARDS OF PERFORMANCE FOR NEW STATIONARY SOURCES [24] World Health Organization, 1989. "Indoor air quality: organic pollutants." Report on a WHO Meeting, Berlin, 23-27 August 1987. EURO Reports and Studies 111. Copenhagen, World Health Organization Regional Office for Europe.
