高效液相色谱法测定洗发护发产品中18种防腐剂和去屑剂

doi:10.3969/j.issn.2097-2806.2024.04.014

摘要/Abstract

摘要：

建立高效液相色谱法（HPLC）同时测定不同基质化妆品中18种防腐剂和去屑剂组分的含量，并对50批市售洗发护发类化妆品进行质量分析。不同基质样品经前处理提取后，采用HPLC法分析，外标法定量。选取C18色谱柱（4.6 mm×250 mm，5 μm），甲醇和磷酸二氢钠水溶液（pH调节至3.8）作为流动相，进行梯度洗脱，流速为1.0 mL/min，柱温30 ℃，选取二极管阵列检测器多波长分析。18种组分在色谱图中分离度良好，峰面积与质量浓度在0.4~600 μg/mL范围内呈良好的线性关系（r>0.998 3），检出浓度在0.4~10 mg/kg之间。多种组分平均回收率（n=6）为83.1%~110.4%，RSD为0.12%~7.6%，回收率良好；多种组分在24 h内保持稳定，RSD在0.15%~3.8%之间，稳定性良好。50批样品中检出9种成分，吡硫鎓锌、吡罗克酮乙醇胺盐、对氯间甲酚、氯咪巴唑、三氯生、水杨酸的含量分别为2 100~6 800，39~2 900，130~370，24~1 600，0.14~0.19，28~1 900 mg/kg。苄氯酚、邻氨基苯酚、邻伞花烃-5-醇的含量检出但是含量小于定量限，无法准确定量。该方法经方法学验证，可同时测定化妆品中18种防腐剂和去屑剂组分的含量。

关键词: 防腐剂, 去屑剂, 高效液相色谱

Abstract:

A high performance liquid chromatography （HPLC） method for simultaneous determination of 18 preservatives and anti-dandruff components in cosmetics of different bases was established, and the quality of 50 batches of commercially available shampoo and hair care cosmetics was analyzed. After the extraction of samples of different bases, the samples were analyzed by HPLC and quantified by external standard method. A C18 column （4.6 mm×250 mm, 5 μm） was used and an aqueous mixture of methanol and sodium dihydrogen phosphate （pH adjusted to 3.8） was selected as mobile phase for gradient elution. The flow rate was 1.0 mL/min. The column temperature was 30 ℃. The chromatographic separation of the 18 components was good. The linearity between peak area and mass concentration was good （r>0.998 3） in the range of 0.4-600 μg/mL, and the detection limit was 0.4-10 mg/kg. The average recoveries （n=6） were 83.1%-110.4%, the RSDs were 0.12%-7.6%, and the recoveries were good. These components remained stable within 24 h with RSDs ranging from 0.15% to 3.8%, indicative of good stability. Nine components were detected in 50 batches of samples, including pyrithione zinc, piroctone olamine, p-chloro-m-cresol, climbazole, triclosan and salicylic acid, whose content was 2 100-6 800, 39-2 900, 130-370, 24-1 600, 0.14-0.19, 28-1 900 mg/kg, respectively. Benzyl chlorophenol, o-aminophenol and o-cymen-5-ol were detected, but their content was less than the limit of quantitation and thus could not be accurately quantified. Therefore, this method could be used to simultaneously determine the 18 antiseptic and anti-dandruff components in cosmetics.

Key words: preservative, anti-dandruff agent, high performance liquid chromatography

中图分类号:

TQ658

祝壮飞, 徐勤科, 刘婷媛, 孙莺, 雷虹. 高效液相色谱法测定洗发护发产品中18种防腐剂和去屑剂[J]. 日用化学工业（中英文）, 2024, 54(4): 477-483.

Zhuangfei Zhu, Qinke Xu, Tingyuan Liu, Ying Sun, Hong Lei. Determination of 18 preservatives and anti-dandruff agents in shampoo and hair care products by HPLC[J]. China Surfactant Detergent & Cosmetics, 2024, 54(4): 477-483.

图/表 4

表1

图1

表2

表3

18种组分的回收率和RSD（n=6）"

组分名称	添加量/μg	回收率/%			RSD/%
组分名称	添加量/μg	粉基质	蜡基质	其他基质	粉基质	蜡基质	其他基质
ZiP	0.2	85.1	84.8	89.1	4.7	4.3	2.6
	2	89.3	86.2	95.7	3.6	2.6	1.9
	10	96.4	92.1	108.4	0.98	0.62	1.1
2，4-DiA	0.2	88.5	89.3	90.2	3.8	4.8	4.1
	2	95.2	95.8	98.5	1.7	3.8	2.6
	10	98.3	93.3	101.4	1.2	2.9	1.4
MeB	0.2	90.4	91.8	92.4	3.1	5.2	2.4
	2	95.6	95.3	95.3	1.9	4.1	1.2
	10	101.5	99.6	104.6	0.38	2.8	0.14
PeS	0.2	86.5	86.2	95.7	4.4	3.7	2.4
	2	95.7	88.3	94.8	2.4	3.4	0.87
	10	97.8	95.4	99.6	1.8	1.7	0.32
BeC	0.2	88.9	90.1	86.8	3.7	4.6	3.6
	2	90.6	92.3	96.3	1.7	3.7	1.9
	10	93.6	94.3	98.8	0.45	1.3	1.1
IbC	0.2	86.7	88.3	96.7	4.4	4.7	4.9
	2	95.8	94.7	93.8	4.1	3.6	3.7
	10	99.5	97.2	106.2	2.9	2.8	1.4
p-TcC	0.2	92.5	91.5	96.3	2.2	2.8	3.4
	2	98.6	98.5	93.2	1.5	2.2	1.6
	10	100.4	101.3	98.9	0.12	0.8	1.1
o-PhP	0.2	85.9	88.4	87.2	3.7	3.7	4.8
	2	94.9	95.3	92.2	1.4	2.8	4.1
	10	95.3	97.5	97.8	0.23	2.1	3.8
Or-5-O	0.2	87.5	89.5	86.7	3.6	4.4	2.5
	2	94.1	97.4	93.4	1.8	3.7	0.96
	10	98.6	95.1	98.6	1.5	3.1	0.55
ChX	0.2	87.8	90.3	92.5	3.2	4.7	2.6
	2	89.4	94.3	99.6	4.5	3.6	1.9
	10	95.1	92.1	100.7	3.7	0.98	1.1
ClB	0.2	88.5	86.3	90.6	7.2	3.8	4.1
	2	95	89.1	98.9	5.5	1.7	2.6
	10	98.4	91.7	99.6	3.5	1.2	1.4
TrC	0.2	92.8	94.3	95.3	4.4	3.1	2.4
	2	98.5	98.2	98.6	3.1	1.9	1.2
	10	103.5	101.2	96.4	1.4	0.38	0.14
TrS	0.2	95.6	89.8	94.6	3.3	4.4	2.4
	2	98	93.8	99.8	2.5	2.4	0.87
	10	98.6	106.2	110.4	0.8	1.8	0.32
SoA	0.2	86.3	93.9	90.6	3.6	3.7	3.6
	2	88.6	94.2	95.7	2.2	1.7	1.9
	10	93.4	98.7	91.8	1.5	0.45	1.1
SaA	0.2	85.3	86.2	96.7	6.2	4.4	4.9
	2	90.5	94.9	93.8	4.8	4.1	3.7
	10	96.7	103.2	104.7	2.1	2.9	1.4
BrF	0.2	88.5	87.3	94.6	4.2	2.2	3.4
	2	93.7	90.2	90.5	2.6	1.5	1.6
	10	95.8	96.8	98.8	1.1	0.12	1.1
PhA	0.2	84.8	83.1	85.3	7.6	6.2	4.8
	2	86.7	84.7	86.2	5.9	4.8	4.1
	10	91.7	88.4	90.5	4.6	3.9	3.8
2，6-DiA	0.2	92.8	89.4	87.9	4.8	5.2	2.5
	2	98.5	93.7	90.6	3.7	4.8	0.96
	10	97.8	95.8	98.4	1.6	3.6	0.55

表3

参考文献 14

[1]	Li Kaili, He Yibo, Zhu yuan, et al. Common preservatives and development trends in cosmetics[J]. China Detergent Industry, 2022 (7) : 82-88.
[2]	Xing Haiyan, Sun Li, Wu Xu, et al. Simultaneous determination of nine 4-hydroxybenzoate preservatives in cosmetics by high performance liquid chromatography[J]. Stoichiometry of Chemical Analysis, 2021, 30 (5) : 46-50.
[3]	Huang Xiaomei, Yao Kangfei, Qi Yufeng. Research on the application of various plant preservatives in cosmetics[J]. Guangdong Chemical Industry, 2022, 49 (6) : 73-75, 79.
[4]	Ding Xiaoshuang, Song Yuqin, An Baiping. Methodological study on the simultaneous determination of three preservatives in cosmetics by high-performance liquid chromatography[J]. Journal of Daily Chemical Science, 2022, 45 (6) : 17-20.
[5]	Wang Gangli, Zhang Qingsheng. Safety technical specifications for cosmetics[M]. Beijing: People’s Health Publishing House, 2017.
[6]	Chen Yan, Bao Xijun, Yan Xiufang, et al. Simultaneous determination of 16 preservatives, sunscreen, and dandruff removers in cosmetics by high-performance liquid chromatography[J]. Journal of Daily Chemical Industry, 2022, 52 (3) : 337-344.
[7]	Xu Jiaqi, Yang Hongmei, Gong Shengzhao. Simultaneous determination of six preservatives in cosmetics by high performance liquid chromatography[J]. Flavor Essence Cosmetics, 2021 (5) : 51-54.
[8]	Huang Xianglu, Lu Jiacan, Xing Shuxia, et al. Progress in the toxicology and risk assessment of zinc pyrrolium, a cosmetic raw material[J]. Journal of Daily Chemical Industry, 2021, 51 (12) : 1235-1241.
[9]	Gao Jiamin, Dai Jing, Li Hongxia, et al. Simultaneous determination of 17 whitening ingredients in cosmetics by high-performance liquid chromatography[J]. Journal of Pharmaceutical Analysis, 2019, 39 (9) : 1643-1650.
[10]	Li Xin, Li Bangrui, Feng Jiali, et al. Determination of 5 preservatives in cosmetics by high-performance liquid chromatography with evaporative light scattering detector[J]. Chinese Journal of Health Inspection, 2022, 32 (20) : 2458-2461.
[11]	Li Yanjun, Qi Aiming, Xiao Shuxiong, et al. Simultaneous determination of four extracellular preservatives in cosmetics by high performance liquid chromatography[J]. Biochemical Journal, 2022, 8 (3) : 54-58.
[12]	Lu Duanping, Chen Shuo, Cheng Jiahua, et al. Determination of two preservatives in three common washing cosmetics by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Physical and Chemical Examination (Chemical Division), 2021, 57 (11) : 961-969.
[13]	Qin Xiufang, Hu Xiuxue, Zhu Tianqing, et al. Progress in the application of chemical preservatives in cosmetics[J]. Chemical Management, 2021 (22) : 66-67.
[14]	Shi Xinghong, Li Jiafu, Cao Feifei, et al. Investigation on the use of 14 preservatives in acne removing cosmetics[J]. Guangzhou Chemical Industry, 2021, 49 (14) : 80-82.

序号	名称	英文缩写	纯度/%	批号	生产商
1	水杨酸	SaA	98.9	G146757	Dr.Ehrenstorfer公司
2	氯咪巴唑	ClB	99.4	G131864	Dr.Ehrenstorfer公司
3	山梨酸	SoA	99.18	G996530	Dr.Ehrenstorfer公司
4	苯氧异丙醇	PhA	99.8	G766231	Dr.Ehrenstorfer公司
5	对氯间甲酚	p-TcC	99.7	G168075	Dr.Ehrenstorfer公司
6	邻苯基苯酚	o-PhP	99	G451296	Dr.Ehrenstorfer公司
7	氯二甲酚	ChX	99.16	G1074553	Dr.Ehrenstorfer公司
8	苄氯酚	BeC	95.4	G1018113	Dr.Ehrenstorfer公司
9	三氯卡班	TrC	99	G161921	Dr.Ehrenstorfer公司
10	三氯生	TrS	99.9	G171100	Dr.Ehrenstorfer公司
11	溴氯芬	BrF	99.52	G1010500	Dr.Ehrenstorfer公司
12	吡硫鎓锌	ZiP	99.2	1217-RB-0018	Cato Resarch Chemicals Inc公司
13	吡罗克酮乙醇胺盐	PeS	94.3	1020-RB-0020	Cato Resarch Chemicals Inc公司
14	2，6-二氯苯甲醇	2，6-DiA	99.4	0312-RC-0027	Cato Resarch Chemicals Inc公司
15	碘丙炔醇丁基氨甲酸酯	IbC	98.6	0729-RB-0040	Cato Resarch Chemicals Inc公司
16	2，4-二氯苯甲醇	2，4-DiA	99.7	0315-RC-0023	Cato Resarch Chemicals Inc公司
17	邻伞花烃-5-醇	Or-5-O	99.7	0312-RC-0029	Cato Resarch Chemicals Inc公司
18	苯甲酸甲酯	MeB	97	1-LXM-88-1	TRC公司

组分名称	检测波长/nm	线性方程	R	线性范围/（μg/mL）	检出限/（mg/kg）	定量限/（mg/kg）
ZiP	280	Y=29.867 00X-66.233 49	0.999 8	0.4~40	10	33
2，4-DiA	230	Y=15.329 04X-25.179 18	0.999 7	2~200	4.0	13
MeB	230	Y=49.411 24X+20.717 79	0.998 3	0.6~60	1.0	3.3
PeS	230	Y=8.355 44X-17.555 09	0.999 3	2~200	4.0	13
BeC	230	Y=20.147 58X+9.682 67	0.998 5	0.6~60	1.0	3.3
IbC	230	Y=0.941 34X-5.551 40	0.999 5	6~600	10	33
p-TcC	230	Y=27.168 06X+11.895 84	0.998 4	0.6~60	1.0	3.3
o-PhP	230	Y=26.860 53X+12.842 60	0.998 5	0.6~60	1.0	3.3
Or-5-O	280	Y=5.903 64X+2.866 09	0.998 3	0.6~60	1.0	3.3
ChX	280	Y=5.475 42X-12.102 30	0.999 5	2~200	4.0	13
ClB	230	Y=13.824 46X-28.376 21	0.999 5	2~200	4.0	13
TrC	280	Y=29.170 38X+4.513 12	0.998 5	0.2~20	0.40	1.3
TrS	280	Y=9.176 35X+3.998 74	0.998 5	0.6~60	1.0	3.3
SoA	280	Y=53.697 87X+8.515 56	0.998 4	0.2~20	0.40	1.3
SaA	280	Y=6.956 37X+0.888 96	0.999 6	0.6~60	2.0	6.7
BrF	230	Y=21.565 52X+11.066 49	0.998 4	0.6~60	1.0	3.3
2，6-DiA	230	Y=6.465 14X-9.815 10	0.999 7	2~200	4.0	13
PhA	280	Y=1.921 07X+0.555 96	0.998 3	0.6~60	2.0	6.7

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