一测多评法测定淋洗类化妆品中23种防腐剂的含量

doi:10.3969/j.issn.2097-2806.2025.10.015

Abstract

Abstract:

A quantitative analysis of multi-components by single marker （QAMS） method for the determination of 23 preservatives in rinse-off cosmetics was established. Samples were extracted with 50% methanol aqueous solution, and 23 preservatives were separated and detected on a C₁₈ column by high performance liquid chromatography （HPLC） with gradient elution. 4-Hydroxybenzoic acid methyl ester was selected as the internal reference substance. The relative time and the relative correction factors of the other 22 kinds of preservatives were established to calculate the content of each component. The results show that the 22 kinds of preservatives have good linear relationships within a certain mass concentration range, and the correlation coefficients （r²） are all greater than 0.999. The limits of detection （LOD） are in the range of 0.033-4.0 μg/g. The solutions remain relatively stable within 7 days. The results of the relative standard deviation （RSD） of each component are between 1.6% and 2.7%. The quantitative analysis of multi-components by a single-marker （QAMS） method and the external standard method have good consistency in the measurement results, and the relative average deviations are between 0.21% and 4.9%. Therefore, this method can be used for the determination and quality control of 23 preservatives in rinse-off cosmetics.

Key words: rinse-off cosmetics, preservatives, quantitative analysis of multi-components by single marker, high performance liquid chromatography

CLC Number:

TQ658

Zhishan Wu,Chengjun Jiang,Weicheng Yin,Yanchao Wang,Jiaojiao Wu,Shuai Yin,Xiaohong Pan. Determination of 23 preservatives in rinse-off cosmetics with quantitative analysis of multi-components by single marker[J].China Surfactant Detergent & Cosmetics, 2025, 55(10): 1344-1351.

Figures/Tables 7

Tab 1

Tab. 2

Mass concentration of standard solution series of 23 components"

序号	化合物名称	质量浓度/（μg/mL）
序号	化合物名称	线性1	线性2	线性3	线性4	线性5	线性6
1	甲基氯异噻唑啉酮	0.040 1	0.200 4	1.002 1	5.010 4	10.020 8	20.041 5
2	甲基异噻唑啉酮	0.086 7	0.433 6	2.167 9	10.839 7	21.679 5	43.359 0
3	2-溴-2-硝基丙烷-1, 3-二醇	1.102 1	5.510 6	27.552 8	137.763 9	275.527 8	551.055 7
4	苯甲醇	2.596 6	12.982 8	64.914 0	324.570 0	649.140 0	1 298.280 0
5	苯氧乙醇	1.256 8	6.283 8	31.419 0	157.095 2	314.190 4	628.380 7
6	氯苯甘醚	0.285 1	1.425 4	7.127 0	35.634 9	71.269 8	142.539 6
7	脱氢乙酸	0.298 4	1.492 1	7.460 5	37.302 7	74.605 3	149.210 6
8	5-溴-5-硝基-1, 3-二噁烷	1.706 9	8.534 3	42.671 6	213.358 0	426.716 0	853.432 0
9	4-羟基苯甲酸	0.185 3	0.926 3	4.631 4	23.156 8	46.313 6	92.627 3
10	4-羟基苯甲酸甲酯	0.108 4	0.542 0	2.710 1	13.550 7	27.101 5	54.203 0
11	羟苯乙酯	0.155 6	0.777 9	3.889 3	19.446 5	38.893 0	77.786 0
12	4-羟基苯甲酸丙酯	0.189 5	0.947 6	4.738 2	23.691 2	47.382 5	94.764 9
13	4-羟基苯甲酸丁酯	0.183 3	0.916 3	4.581 7	22.908 6	45.817 1	91.634 3
14	4-羟基苯甲酸异丙酯	0.146 7	0.733 5	3.667 4	18.337 2	36.674 5	73.348 9
15	4-羟基苯甲酸苯酯	0.164 2	0.820 9	4.104 7	20.523 6	41.047 2	82.094 3
16	4-羟基苯甲酸异丁酯	0.170 1	0.850 3	4.251 6	21.258 0	42.516 1	85.032 1
17	4-羟基苯甲酸苄酯	0.123 8	0.618 9	3.094 3	15.471 7	30.943 5	61.887 0
18	4-羟基苯甲酸戊酯	0.465 3	2.326 7	11.633 5	58.167 7	116.335 5	232.670 9
19	苯甲酸	0.522 3	2.611 4	13.056 9	65.284 7	130.569 3	261.138 6
20	苯甲酸乙酯	0.416 3	2.081 3	10.406 7	52.033 7	104.067 4	208.134 9
21	苯甲酸丙酯	0.426 5	2.132 4	10.661 8	53.308 9	106.617 8	213.235 5
22	苯甲酸异丙酯	0.428 9	2.144 7	10.723 6	53.618 0	107.236 1	214.472 1
23	苯甲酸苯基酯	0.389 0	1.945 1	9.725 4	48.627 2	97.254 5	194.509 0

Tab. 2

Fig. 1

Tab. 3

Regression equations, linear ranges, correlation coefficients（r2）, LODs and LQDs of the preservatives"

序号	化合物名称	线性方程	线性范围/（mg/L）	r²	检出限/ （μg/g）	定量限/ （μg/g）
1	甲基氯异噻唑啉酮	y=0.410 4 x+0.031 6	0.040 1~20.041 5	0.999 7	0.033	0.11
2	甲基异噻唑啉酮	y=0.468 2 x-0.021 0	0.086 7~43.359 0	0.999 3	0.071	0.24
3	2-溴-2-硝基丙烷-1, 3-二醇	y=0.048 8 x-0.177 9	1.102 1~551.055 7	0.999 8	2.8	9.2
4	苯甲醇	y=0.013 7 x-0.078 2	2.596 6~1 298.280 0	0.999 7	4.0	13
5	苯氧乙醇	y=0.045 7 x-0.085 1	1.256 8~628.380 7	0.999 5	1.2	3.9
6	氯苯甘醚	y=0.519 0 x-0.296 8	0.285 1~142.539 6	0.999 6	0.11	0.36
7	脱氢乙酸	y=0.202 7 x-0.164 1	0.298 4~149.210 6	0.999 5	0.32	1.1
8	5-溴-5-硝基-1, 3-二噁烷	y=0.051 1 x-0.153 6	1.706 9~853.432 0	0.999 6	1.6	5.4
9	4-羟基苯甲酸	y=1.031 5 x-0.488 1	0.185 3~92.627 3	0.999 6	0.062	0.21
10	4-羟基苯甲酸甲酯	y=1.394 2 x-0.352 4	0.108 4~54.203 0	0.999 6	0.04	0.13
11	4-羟基苯甲酸乙酯	y=1.080 0 x-0.381 8	0.155 6~77.786 0	0.999 6	0.052	0.17
12	4-羟基苯甲酸丙酯	y=1.117 1 x-0.464 6	0.189 5~94.764 90	0.999 6	0.052	0.17
13	4-羟基苯甲酸丁酯	y=1.076 3 x-0.386 5	0.183 3~91.634 3	0.999 5	0.14	0.48
14	4-羟基苯甲酸异丙酯	y=1.071 6 x-0.299 9	0.146 7~73.348 9	0.999 5	0.053	0.18
15	4-羟基苯甲酸苯酯	y=1.182 0 x-0.445 9	0.164 2~82.094 3	0.999 6	0.064	0.21
16	4-羟基苯甲酸异丁酯	y=1.067 3 x-0.304 8	0.170 1~85.032 1	0.999 4	0.11	0.36
17	4-羟基苯甲酸苄酯	y=1.155 8 x-0.297 7	0.123 8~61.887 0	0.999 5	0.14	0.45
18	4-羟基苯甲酸戊酯	y=1.043 4 x-0.410 1	0.465 3~232.670 9	0.999 1	0.086	0.29
19	苯甲酸	y=0.807 0 x-0.638 1	0.522 3~261.138 6	0.999 4	0.12	0.41
20	苯甲酸乙酯	y=0.903 7 x-0.858 6	0.416 3~208.134 9	0.999 7	0.29	0.98
21	苯甲酸丙酯	y=0.884 9 x-0.830 4	0.426 5~213.235 5	0.999 7	0.17	0.55
22	苯甲酸异丙酯	y=0.897 0 x-0.824 3	0.428 9~214.472 1	0.999 7	0.18	0.59
23	苯甲酸苯基酯	y=1.212 1 x-0.808 5	0.389 0~194.509 0	0.999 5	0.084	0.28

Tab. 3

Tab 4

Tab. 5

Tab. 6

References 13

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序号	对照品名称	来源	含量
1	甲基氯异噻唑啉酮	德国Dr.Ehrenstorfer公司	98.5%
2	甲基异噻唑啉酮	上海安谱璀世标准技术服务有限公司	99.0%
3	2-溴-2-硝基丙烷-1, 3-二醇	上海安谱璀世标准技术服务有限公司	97.6%
4	苯甲醇	中国食品药品检定研究院	99.7%
5	苯氧乙醇	德国Dr.Ehrenstorfer公司	99.3%
6	氯苯甘醚	德国Dr.Ehrenstorfer公司	99.8%
7	脱氢乙酸	ANPEL-Trace	99.9%
8	5-溴-5-硝基-1, 3-二噁烷	上海源叶生物科技有限公司	99.9%
9	4-羟基苯甲酸	中国食品药品检定研究院	100.0%
10	4-羟基苯甲酸甲酯	中国食品药品检定研究院	99.9%
11	羟苯乙酯	中国食品药品检定研究院	100.0%
12	4-羟基苯甲酸丙酯	中国食品药品检定研究院	99.9%
13	4-羟基苯甲酸丁酯	上海安谱璀世标准技术服务有限公司	99.2%
14	4-羟基苯甲酸异丙酯	上海安谱璀世标准技术服务有限公司	100.1%
15	4-羟基苯甲酸苯酯	上海安谱璀世标准技术服务有限公司	99.0%
16	4-羟基苯甲酸异丁酯	上海安谱璀世标准技术服务有限公司	99.3%
17	4-羟基苯甲酸苄酯	中国食品药品检定研究院	99.1%
18	4-羟基苯甲酸戊酯	上海安谱璀世标准技术服务有限公司	99.9%
19	苯甲酸	中国食品药品检定研究院	99.9%
20	苯甲酸乙酯	德国CNW公司	99.0%
21	苯甲酸丙酯	上海源叶生物科技有限公司	98.0%
22	苯甲酸异丙酯	广州佳途科技股份有限公司	99.9%
23	苯甲酸苯基酯	上海源叶生物科技有限公司	99.0%

序号	化合物名称	f_si
序号	化合物名称	线性1	线性4	线性6	平均值	RSD/%
1	甲基氯异噻唑啉酮	3.22	3.18	3.19	3.20	0.75
2	甲基异噻唑啉酮	2.96	2.81	2.80	2.86	3.04
3	2-溴-2-硝基丙烷-1, 3-二醇	32.35	30.76	31.77	31.62	2.54
4	苯甲醇	105.88	102.02	103.76	103.89	1.86
5	苯氧乙醇	30.41	28.85	30.22	29.83	2.85
6	氯苯甘醚	2.78	2.69	2.68	29.83	2.85
7	脱氢乙酸	7.06	6.94	6.81	6.94	1.86
8	5-溴-5-硝基-1, 3-二噁烷	28.72	27.45	27.68	27.95	2.42
9	4-羟基苯甲酸	1.39	1.36	1.36	1.37	1.07
10	4-羟基苯甲酸乙酯	1.25	1.29	1.29	1.28	1.85
11	4-羟基苯甲酸丙酯	1.23	1.26	1.25	1.25	0.88
12	4-羟基苯甲酸丁酯	1.50	1.54	1.51	1.52	1.41
13	4-羟基苯甲酸异丙酯	1.36	1.40	1.37	1.38	1.34
14	4-羟基苯甲酸苯酯	1.22	1.19	1.18	1.20	1.44
15	4-羟基苯甲酸异丁酯	1.70	1.66	1.65	1.67	1.80
16	4-羟基苯甲酸苄酯	0.86	0.88	0.87	0.87	0.86
17	4-羟基苯甲酸戊酯	1.36	1.28	1.28	1.31	3.61
18	苯甲酸	1.76	1.70	1.75	1.31	3.61
19	苯甲酸乙酯	1.55	1.56	1.55	1.55	0.39
20	苯甲酸丙酯	1.65	1.57	1.56	1.59	3.19
21	苯甲酸异丙酯	1.65	1.55	1.55	1.58	3.85
22	苯甲酸苯基酯	1.19	1.13	1.14	1.15	2.89

组分名称	含量/（μg/g）
	样品1			样品2			样品3
	QAMS	EMS	RAD/%	QAMS	EMS	RAD/%	QAMS	EMS	RAD/%
甲基异噻唑啉酮	0.45	0.46	2.51	0.29	0.29	1.68	4.83	5.00	6.79
甲基氯异噻唑啉酮	0.93	0.91	1.69	0.56	0.54	3.38	—	—	—
苯甲醇	—	—	—	—	—	—	—	—	—
苯氧乙醇	—	—	—	235.91	245.67	4.05	—	—	—
5-溴-5-硝基-1, 3-二噁烷	14.55	14.77	3.05	—	—	—	—	—	—
4-羟基苯甲酸丙酯	73.70	73.70	0.22	59.55	59.74	0.31	77.40	77.55	0.21
苯甲酸	—	—	—	7.03	7.24	2.89	—	—	—
组分名称	含量/（μg/g）
	样品4			样品5			样品6
	QAMS	EMS	RAD/%	QAMS	EMS	RAD/%	QAMS	EMS			RAD/%
甲基异噻唑啉酮	0.39	0.40	4.14	0.38	0.40	4.41	—	—			—
甲基氯异噻唑啉酮	0.81	0.78	3.04	—	—	—	—	—			—
苯甲醇	—	—	—	101.03	104.26	3.15	92.31	93.46			1.24
苯氧乙醇	—	—	—	763.19	797.53	4.40	733.97	747.20			1.79
5-溴-5-硝基-1, 3-二噁烷	—	—	—	—	—	—	27.48	28.67			4.25
4-羟基苯甲酸丙酯	44.92	45.16	0.54	—	—	—	—	—			—
苯甲酸	—	—	—	—	—	—	6.72	6.96			3.44
组分名称	含量/（μg/g）
	样品7			样品8			样品9
	QAMS	EMS	RAD/%	QAMS	EMS	RAD/%	QAMS	EMS		RAD/%
甲基异噻唑啉酮	0.29	0.30	4.87	—	—	—	0.55	0.56		0.51
甲基氯异噻唑啉酮	0.70	0.67	4.47	—	—	—	—	—		—
苯甲醇	—	—	—	—	—	—	—	—		—
苯氧乙醇	—	—	—	330.14	316.35	4.27	320.58	333.36		3.91
5-溴-5-硝基-1, 3-二噁烷	—	—	—	—	—	—	75.47	76.37		1.19
4-羟基苯甲酸丙酯	74.07	74.23	0.22	—	—	—	—	—		—
苯甲酸	—	—	—	—	—	—	—	—		—

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Determination of 23 preservatives in rinse-off cosmetics with quantitative analysis of multi-components by single marker

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序号	化合物名称	t_si
序号	化合物名称	线性1	线性4	线性6	平均值	RSD/%
1	甲基氯异噻唑啉酮	0.56	0.56	0.56	0.56	0.02
2	甲基异噻唑啉酮	0.19	0.19	0.19	0.19	0.01
3	2-溴-2-硝基丙烷-1, 3-二醇	0.36	0.36	0.36	0.36	0.21
4	苯甲醇	0.77	0.77	0.77	0.77	0.05
5	苯氧乙醇	0.91	0.91	0.91	0.91	0.02
6	氯苯甘醚	1.04	1.04	1.04	1.04	0.03
7	脱氢乙酸	1.07	1.07	1.07	1.07	0.00
8	5-溴-5-硝基-1, 3-二噁烷	1.10	1.10	1.10	1.10	0.02
9	4-羟基苯甲酸	0.58	0.58	0.58	0.58	0.11
10	4-羟基苯甲酸乙酯	1.20	1.20	1.20	1.20	0.02
11	4-羟基苯甲酸丙酯	1.39	1.40	1.40	1.40	0.03
12	4-羟基苯甲酸丁酯	1.60	1.60	1.60	1.60	0.02
13	4-羟基苯甲酸异丙酯	1.37	1.37	1.37	1.37	0.03
14	4-羟基苯甲酸苯酯	1.54	1.54	1.54	1.54	0.02
15	4-羟基苯甲酸异丁酯	1.66	1.66	1.66	1.66	0.02
16	4-羟基苯甲酸苄酯	1.63	1.63	1.63	1.63	0.02
17	4-羟基苯甲酸戊酯	2.27	2.27	2.27	2.27	0.02
18	苯甲酸	0.96	0.96	0.96	0.96	0.06
19	苯甲酸乙酯	1.73	1.73	1.73	1.73	0.05
20	苯甲酸丙酯	2.36	2.36	2.36	2.36	0.04
21	苯甲酸异丙酯	2.33	2.33	2.33	2.33	0.03
22	苯甲酸苯基酯	2.46	2.46	2.46	2.46	0.05