高效液相色谱法同时测定化妆品中16种防腐剂、防晒剂和去屑剂

doi:10.3969/j.issn.1001-1803.2022.03.016

摘要/Abstract

摘要：

建立了高效液相色谱法同时测定化妆品中防腐剂、防晒剂和去屑剂共16种组分的分析方法。样品经甲醇提取后,使用Eclipse Plus C18（250 mm×4.6 mm×5 μm）色谱柱,以甲醇-0.5 mmol/L EDTA-2Na水溶液（pH=3.06）为流动相,梯度洗脱。采用二极管阵列检测器在多波长下同时测定化妆品中10种防腐剂、4种防晒剂和2种去屑剂。该方法的相对标准偏差为2.2%~6.5%,回收率为90.9%~109.7%,16种组分在相应的线性范围内线性关系良好,相关系数范围为0.999 0~0.999 7,该方法具有较高的准确度和精密度,能满足实际检测需求,为实验室检测提供新的技术支持。

关键词: 防腐剂, 防晒剂, 去屑剂, 高效液相色谱法

Abstract:

A method based on HPLC was established for the determination of 16 components in cosmetics including 10 types of preservatives, 4 types of sunscreens and 2 types of anti-dandruffs. The amount of 0.5 g of the cosmetic product was dissolved in methanol in a 10 mL volumetric flask and was ultrasonically extracted for 30 min. The extract was filtered through a 0.22 μm membrane, and then 10 μL solution was introduced onto an Eclipse Plus C18 column （250 mm×0.46 mm×5 μm） with methanol-0.5 mmol/L EDTA-2Na aqueous solution （pH=3.06） as mobile phase by gradient elution. The 16 components were separated at multiple wavelengths of the DAD detector. These preservatives, sunscreen agents and anti-dandruffs could be analyzed within 50 min simultaneously. The external standard method was employed for quantitative determination. The relative standard deviation of the method is 2.2%-6.5%, and the recovery is 90.9%-109.7%. The limits of detection （LODs, S/N=3） and limits of quantification （LOQs,S/N=10） of 16 components were determined. By this method, different extraction solvent, extraction time and mobile phase were compared. Among these, methanol is used as extraction solvent for 30 minutes and methanol-0.5 mmol/LEDTA-2Na aqueous solution （pH=3.06） as mobile phase shows good linear relationship in their respective mass concentration range, with the correlation coefficients higher than 0.999 0. This method has high accuracy and precision. 30 products in the market were analyzed, and the results show that phenoxyethanol, benzoic acid, and methyl 4-hydroxybenzoate are the most commonly added preservatives in cosmetics. For the four sunscreens, octyl 4-methoxycinnamate is the most frequently added. Ketoconazole is not detected in these products. In these products, all of the 16 components are lower than the relevant limits in China. This method provides technical support for market supervision and laboratory testing, which also can meet their practical testing requirements.

Key words: preservative, sunscreen agent, anti-dandruff, HPLC

中图分类号:

TQ658

陈燕,鲍熹珺,闫秀芳,刘建宁,郭芳,牛文霞. 高效液相色谱法同时测定化妆品中16种防腐剂、防晒剂和去屑剂[J]. 日用化学工业, 2022, 52(3): 337-344.

Chen Yan,Bao Xijun,Yan Xiufang,Liu Jianning,Guo Fang,Niu Wenxia. Simultaneous determination of 16 preservatives, sunscreens and anti-dandruffs in cosmetics by HPLC[J]. China Surfactant Detergent & Cosmetics, 2022, 52(3): 337-344.

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参考文献 17

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序号	组分名称（缩写）	分子量	纯度/%	CAS号	分子式
1	甲基异噻唑啉酮（MIT）	115.15	≥99.0	2682-20-4	C₄H₅NOS
2	甲基氯异噻唑啉酮（CIT）	149.56	≥99.0	26172-55-4	C₄H₄ClNOS
3	对羟基苯乙酮（ HBP）	136.15	≥99.0	99-93-4	C₈H₈O₂
4	苯甲醇（BA）	108.13	≥99.9	100-51-6	C₇H₈O
5	P-茴香酸（ PAA）	152.15	≥99.0	100-09-4	C₈H₈O₃
6	水杨酸（ SA）	138.12	≥99.5	69-72-7	C₇H₆O₃
7	苯氧乙醇（ PE）	138.16	≥99.3	122-99-6	C₈H₁₀O₂
8	氯苯甘醚（CHP）	202.63	≥99.3	104-29-0	C₉H₁₁ClO₃
9	4-羟基苯甲酸甲酯（MP）	152.15	≥99.7	99-76-3	C₈H₈O₃
10	4-羟基苯甲酸乙酯（EP）	166.2	≥99.0	120-47-8	C₉H₁₀O₃
11	酮康唑（KTZ）	531.43	≥99.5	65277-42-1	C₂₆H₂₈Cl₂N₄O₄
12	吡罗克酮乙醇胺盐（OCT）	298.42	≥97.0	68890-66-4	C₁₆H₃₀N₂O₃
13	二苯酮-3（BP-3）	228.24	≥99.5	131-57-7	C₁₄H₁₂O₃
14	奥克立林（OC）	361.48	≥98.5	6197-30-4	C₂₄H₂₇NO₂
15	甲氧基肉桂酸乙基己酯（OMC）	290.4	≥98.5	5466-77-3	C₁₈H₂₆O₃
16	水杨酸乙基己酯（EHS）	250.33	≥99.5	118-60-5	C₁₅H₂₂O₃

序号	组分缩写	ρ（标准储备溶液）/ （mg/L）	ρ（STD-1）/ （mg/L）	ρ（STD-2）/ （mg/L）	ρ（STD-3）/ （mg/L）	ρ（STD-4）/ （mg/L）	ρ（STD-5）/ （mg/L）
1	MIT	10 000	10	20	50	100	200
2	CIT	30 000	30	60	150	300	600
3	HBP	10 000	10	20	50	100	200
4	BA	10 420	10.42	20.84	52.1	104.2	208.4
5	PAA	10 340	10.34	20.68	51.7	103.4	206.8
6	SA	10 210	10.21	20.42	51.05	102.1	204.2
7	PE	10 030	10.03	20.06	50.15	100.3	200.6
8	CHP	10 100	10.10	20.2	50.5	101	202
9	MP	8 900	8.90	17.8	44.5	89	178
10	EP	10 020	10.02	20.04	50.1	100.2	200.4
11	KTZ	10 760	10.76	21.52	53.8	107.6	215.2
12	OCT	12 880	12.88	25.76	64.4	128.8	257.6
13	BP-3	10 100	10.10	20.20	50.5	101	202
14	OC	10 015	10.02	20.03	50.08	100.15	200.3
15	OMC	10 320	10.32	20.64	51.6	103.2	206.4
16	EHS	12 610	12.61	25.22	63.05	126.1	252.2

样品类型	组分缩写	甲醇15 min下含量/（mg/kg）	甲醇30 min下含量/（mg/kg）	TFH 15 min下含量/（mg/kg）	TFH 30 min下含量/（mg/kg）	RSD/%
霜	PAA	801	814	795	816	1.3
霜	PE	4 387	4 412	4 356	4 501	1.4
乳液	HBP	4 828	4 833	4 835	4 883	0.5
化妆水	PE	2 256	2 209	2 250	2 231	0.9
化妆水	MP	1 613	1 617	1 611	1 627	0.4
粉底液	HBP	4 778	4 771	4 781	4 796	0.2
防晒乳	OMC	57 726	58 246	57 674	56 901	1.0
	OS	17 387	18 396	17 350	17 345	2.9
	PE	6 014	6 112	5 987	5 758	2.5
	MP	2 213	2 147	2 019	2 001	4.8
洗发水	OCT	3 014	3 030	2 897	3 001	2.0
	MIT	1.34	1.31	1.37	1.30	2.4
	CIT	3.31	3.36	3.26	3.14	2.9

序号	组分缩写	线性范围/（mg/L）	回归方程	相关系数	LODs/（mg/kg）	LOQs/（mg/kg）
1	MIT	10~200	y=20.42x-3.11	0.999 7	0.3	1.0
2	CIT	30~600	y=16.98x-17.90	0.999 7	0.3	1.0
3	HBP	10~200	y=27.93x-10.82	0.999 7	5	10
4	BA	10.42~208.4	y =0.75x-0.09	0.999 4	30	100
5	SA	10.21~204.2	y=30.65x-3.30	0.999 3	10	30
6	PE	10.03~200.60	y=9.13x+0.38	0.999 5	10	30
7	MP	8.9~178	y=60.39x-2.81	0.999 7	5	15
8	PAA	10.34~206.8	y=49.72x-4.79	0.999 7	20	60
9	CHP	10.1~202	y=31.55x-8.14	0.999 7	10	30
10	EP	10.02~200.4	y=51.12x-21.12	0.999 7	5	15
11	KTZ	10.76~215.2	y=21.96x-34.75	0.999 7	10	30
12	BP-3	10.1~202	y=11.62x-6.34	0.999 7	30	90
13	OCT	12.88~257.6	y=6.54x-34.82	0.999 0	20	60
14	OC	10.02~200.3	y=11.62x+2.18	0.999 7	30	90
15	OMC	10.32~206.4	y=12.95x+3.41	0.999 7	50	150
16	EHS	12.61~252.2	y=16.77x-4.46	0.999 7	30	90

序号	组分缩写	加标量/μg	实测值/μg	回收率/%	平均RSD/%
1	MIT	10.0	9.29~10.31	92.9~103.1	2.2
		50.0	49.01~52.98	98.0~106.0
		200.0	191.10~208.03	95.6~104.0
2	CIT	30.0	28.91~31.30	96.4~104.3	3.8
		150.0	150.22~157.32	100.1~104.9
		600.0	560.13~653.38	93.4~108.9
3	HBP	10.0	9.21~10.74	92.1~107.4	3.5
		50.0	49.95~53.70	99.9~107.4
		200.0	191.27~204.27	95.6~102.1
4	BA	10.42	10.25~10.85	98.4~104.1	3.0
		52.10	48.46~52.65	93.0~101.1
		208.40	200.13~226.13	96.0~108.5
5	SA	10.21	9.72~10.33	95.2~101.2	2.8
		51.05	50.11~54.68	98.2~107.1
		204.20	187.13~218.16	91.6~106.8
6	PE	10.03	9.61~10.46	95.8~104.3	4.4
		50.15	48.20~50.37	96.1~100.4
		200.60	190.27~200.66	94.9~100.0
7	MP	8.90	8.65~9.76	97.2~109.7	4.6
		44.50	44.57~46.69	100.2~104.9
		178.00	175.24~190.12	98.5~106.8
8	PAA	10.34	10.13~10.83	98.0~104.7	2.6
		51.70	50.24~54.12	97.2~104.7
		206.80	200.00~224.37	96.7~108.5
9	CHP	10.10	10.18~10.92	100.8~108.1	3.1
		50.50	48.24~53.00	95.5~105.0
		202.00	187.37~206.25	92.8~102.1
10	EP	10.02	9.46~10.80	94.4~107.8	4.9
		50.10	48.26~52.24	96.3~104.3
		200.40	194.13~216.33	96.9~108.0
11	KTZ	10.76	10.01~11.32	93.0~105.2	3.9
		53.80	52.13~56.09	96.9~104.3
		215.20	208.24~233.22	96.9~104.3
12	BP-3	10.10	9.56~10.54	94.7~104.4	6.5
		50.50	46.72~52.54	92.5~104.0
		202.00	190.21~206.24	94.2~102.1
13	OCT	12.88	12.43~13.56	96.5~105.3	4.7
		64.40	60.15~68.96	93.4~107.1
		257.60	234.26~258.37	90.9~100.3
14	OC	10.015	9.51~10.91	95.0~108.9	5.2
		50.075	46.72~51.97	93.3~103.8
		200.30	186.24~215.22	93.0~107.5
15	OMC	10.32	10.08~10.73	97.7~104.0	4.4
		51.60	48.56~54.41	94.1~105.5
		206.40	195.25~225.11	94.6~109.1
16	EHS	12.61	11.87~13.05	94.1~103.5	4.3
		63.05	58.13~66.52	92.2~105.5
		252.20	232.70~255.12	92.3~101.2