异噻唑啉酮类防腐剂标准现状及检测技术研究进展

doi:10.3969/j.issn.2097-2806.2023.10.010

Abstract

Abstract:

Isothiazolinone preservatives are broad-spectrum, high-efficiency and environmentally friendly, which have been widely used in cosmetics, toys, coatings and other fields. However, there are more and more reports at home and abroad about allergic reactions, contact dermatitis, and even chemical skin burns caused by isothiazolinone preservatives, which has aroused concerns in society. It is of great significance to pay attention to the relevant regulations and standards of isothiazolinone preservatives and select accurate and efficient analytical methods for their safety risk assessments. Herein, a comprehensive overview on the limits of content of isothiazolinone preservatives in European Union and China was made, as well as the domestic situation of detection standards. The pretreatment techniques, including accelerated solvent extraction, solid-phase extraction, and QuEChERS, were briefly reviewed. The applications of gas chromatography, gas chromatography-mass spectrometry, liquid chromatography, and liquid chromatography-tandem mass spectrometry for isothiazolinone preservatives were reviewed. Finally, the development direction of detection techniques for isothiazolinone preservatives in different products was prospected, in order to provide reference to related researchers and improve the relevant standard system.

Key words: isothiazolinone preservative, application, standard, detection technique, review

CLC Number:

TQ658

He Xiaoling, Ma Yan, Deng Xing, Lu Jiali, Wu Rongrong, Long Mei. Current status of standards and research progress of detection methods of isothiazolinone preservatives[J].China Surfactant Detergent & Cosmetics, 2023, 53(10): 1186-1193.

Figures/Tables 3

Tab. 1

Tab. 2

Tab. 3

Comparison of some representative detection methods"

产品	分析物质	前处理技术	分析技术	色谱柱	检出限	回收率/%	精密度/%	参考文献
化妆品	MIT、CMIT	LLE	HPLC-DAD	Apollo Phenyl column	0.03, 0.090 mg/mL	86.5~101.8	2.5~5.2	[23]
烟用香精香料	MIT、CMIT	OE	HPLC-MS/MS	Agilent ZORBAX 300SB-C8	3.2, 3.6 μg/L	77.1~95.0	1.0~5.0	[24]
水性涂料	MIT、CMIT、BIT、OIT、DCOIT	UE	HPLC-MS/MS	Agilent Zorbax Eclipse Plus C18	0.001 3~0.420 0 mg/kg	86.73~93.6	2.3~5.8	[25]
纺织品	OIT等	ASE	HPLC-DAD	Agilent 1200 C18	LOQ：0.16 mg/kg	94.9~97.3	7.3~8.4	[26]
纺织品	OIT等	ASE	GC-MS	DB-1MS	LOQ：0.09 mg/kg	96.7~97.9	5.4~6.3	[26]
皮革及制品	MIT、CMIT、BIT、BBIT、MBIT、OIT、DCOIT	SPE	GC-MS	RXi-5MS	OIT, MBIT, BBIT: 0.05 mg/kg；MIT, CMIT, BIT, DCOIT：0.10 mg/kg	80.21~95.87	1.26~4.85	[27]
烟用纸	MIT、CMIT	DSPE	GC-MS	HP-5MS	0.007，0.012 μg/mL	92.59~107.62	1.32~7.99	[28]
个人护理用品	MIT、CMIT等	UE	HPLC-DAD-FLD	KromaPhase 5μm C18	11，55 μg/L	80~113	0.9, 2.2	[40]
保健品	MIT、CMIT等	UE	GC-MS	DB-624UI	0.002 mg/L	96.2~107.6	0.4~5.3	[41]
家用液体洗涤剂	MIT、CMIT、BIT、DCOIT	UE	UPLC- MS/MS	Waters ACQUITY UPLC HSS T3 C18	0.05 mg/kg	81.2~103.2	2.23~4.52	[42]
木材及木制品	MIT、CMIT、BIT	UE	HPLC-MS/MS	Eclipse Plus C18	0.04，0.13，0.12 mg/kg	85~111	0.93~8.20	[43]
湿纸巾	MIT、CMIT、BIT、OIT、DCOIT	QuEChERS	UPLC-MS/MS	Waters ACQUITY UPLC HSS T3 C18	LOQ：0.005 mg/kg	91.1~103.5	2.11~3.27	[44]
水基胶	MIT、CMIT	TP-HF-LPME	HPLC-DAD	Waters Prontosil 120-5-C18 AQ	0.037~0.147 μg/g	102~103	1.2~11.7	[45]
水基胶	MIT、CMIT	TP-HF-LPME	UPLC-Q-TOF-MS	Waters UPLCBEH C18	0.004~0.007 μg/g		2.4~4.1	[45]
再造烟叶	MIT、CMIT	QuEChERS	HPLC-MS/MS	Agilent ZORBAX 300SB-C8	LOQ：2.5，2.8 μg/L	90.2~98.3	1.0~5.0	[46]
饲料	MIT、CMIT、BIT	SPE	HPLC-MS/MS	Eclipse Plus C18	0.010~0.015 mg/L	75.8~102	1.63~5.75	[47]
海水	BIT、OIT、DCOIT等	SPE	HPLC-DAD	Agilent Eclipse XDB-C18	1.7×10^-6，3.6×10^-7，2.5×10^-7mol/L	96~110	<4	[48]

Tab. 3

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Current status of standards and research progress of detection methods of isothiazolinone preservatives

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产品	法规/标准	MIT	CMIT	BIT	CMIT/MIT混合物（质量比3∶1）	OIT	参考文献
化妆品	（EC） No 1223/2009	0.001 5% （淋洗类产品）	—	—	0.001 5% （淋洗类产品）	—	[8?-10]
	（EU） 2016/1198
	（EU） 2017/1224
玩具	EN 71-9-2005+A1-2007	10 mg/kg	10 mg/kg	15 mg/kg	—	—	[11??-14]
	EN 71-10-2005	10 mg/kg	10 mg/kg	15 mg/kg	—	—
	（EU） 2015/2116	0.25 mg/kg	0.75 mg/kg	5 mg/kg	1 mg/kg	—
	（EU） 2015/2117	0.25 mg/kg	0.75 mg/kg	5 mg/kg	1 mg/kg	—
油漆涂料	2014/312/EU	0.02%	—	0.05%	0.001 5%	0.05%	[15]
食品接触材料-塑料	（EC） No 1935/2004	0.5 mg/kg （SML）	—	—	—	—	[16,17]
食品接触材料-塑料	（EU） No 10/2011	0.5 mg/kg （SML）	—	—	—	—	[16,17]
手洗餐具用洗涤剂	（EU） 2017/1214	0.005 0%	—	0.005 0%	0.001 5%	—	[18]

产品		MIT	CMIT	BIT	CMIT/MIT混合物（质量比3∶1）	OIT	DCOIT	参考文献
化妆品		0.01%	—	—	0.001 5% （淋洗类产品）	—	—	[19]
食品接触材料及制品	胶粘剂	0.5 mg/kg （SML）（水基型）	—	1.2 mg/kg （SML）	—	—	—	[20]
	纸制品	0.005% （最大使用量）；0.5 mg/kg （SML）	0.005%	0.16 mg/dm² （最大使用量）； 1.2 mg/kg （SML）	0.005%	—	—
	油墨	—	—	0.02 % （最大使用量）；1.2 mg/kg （SML）	—	—	—
	涂料	0.002 5% （最大使用量）；0.5 mg/kg （SML）（水基型）	0.002 5%	—	0.002 5%	—	—
	塑料	—	PA、PE、PP、PS、ABS、PET、PC （按需适量使用）	—	PA、PE、PP、PS、ABS、PET、PC （按需适量使用）	—	—
	橡胶	—	—	0.02% （最大使用量）； 1.2 mg/kg （SML）		—	—
牙膏用原料		0.01%	—	—	0.001 5%	—	—	[21]
涂料		200 mg/kg	—	500 mg/kg	15 mg/kg	500 mg/kg	500 mg/kg	[22]
涂料		总量不得超过 750 mg/kg						[22]

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