高效液相色谱法同时测定防晒类化妆品中23种禁限用组分的含量

doi:10.3969/j.issn.1001-1803.2021.10.014

Abstract

Abstract:

High performance liquid chromatography （HPLC） method for simultaneous determination of 23 prohibited or restricted components in sunscreen cosmetics was established. The sample was dissolved and mixed with tetrahydrofuran or a mixed solvent, extracted by sonicating for 30 min, diluted with tetrahydrofuran or a mixed solvent, and filtered by a microporous membrane. For HPLC analysis, the sample was separated by Kromasil C₁₈ column, and gradient elution was performed with 0.1% formic-methanol-tetrahydrofuran as the mobile phase, with the flow rate of 1.0 mL/min, column temperature of 35 ℃, detection wavelength of 311 nm. The quantitative determination was applied by standard curve method. The results show that there is a good linear relationship between the concentration of 23 prohibited or restricted components and the peak area is in a certain range, with the R values all greater than 0.998 4. The detection limits of the method are 0.01%-0.04%. At low and high spiked levels, the recoveries of the two substrates （sunscreen and lip balm） ranged from 85.6%-113.2%, with RSDs ranging from 0.4%-5.4%. This method is optimized on the basis of the loading method in Safety and Technical Standards for Cosmetics （2015 Edition）, so that the stability of each component in the detection process is better. On the basis of the “specification” detection method in this paper, the extraction solvent and the kind of mobile phase of the test sample solution is optimized. The new method can simultaneously determine amino acid and diphenyl ketone-2 of 23 kinds of sunscreen, improve the efficiency of the detection, enhance the stability of the component under test condition and ensure the stability of the measured component accuracy. In this paper, HPLC method was used to establish a simultaneous detection method for 23 kinds of prohibited or restricted sunscreen substances, and the extraction solvents and mobile phase types of the tested solutions were optimized. The new method overcomes the inaccuracy of the detection results caused by the easy oxidation of cresol trazole trisiloxane and other contained detection methods in the Code. The new method can simultaneously determine 23 kinds of sunscreens such as p-aminobenzoic acid and diphenylketone-2, which greatly improves the detection efficiency. The new method is proved to be accurate and repeatable, and is suitable for the inspection and detection of sunscreen cosmetics.

Key words: high performance liquid chromatography, sunscreen cosmetics, prohibited or restricted components

CLC Number:

TQ658

Shang Shu,Feng Youlong,Fang Fang. Simultaneous determination of 23 prohibited or restricted components in sunscreen cosmetics by high performance liquid chromatography[J].China Surfactant Detergent & Cosmetics, 2021, 51(10): 1018-1025.

Figures/Tables 6

Tab. 1

Tab. 2

Fig. 1

Tab. 3

Linear equation, linear range, LOD and LOQ"

序号	对照品名称	线性方程	线性范围/（μg·mL^-1）	相关系数	检出限/%	定量限/%
20	苯基苯并咪唑磺酸（以酸计）	Y=0.545 9X+0.285 1	1.88~93.91	0.999 5	0.006	0.019
22	对氨基苯甲酸	Y=0.198 4X-0.185 2	5.00~100.10	0.999 2	0.015	0.100
21	对苯二亚甲基二樟脑磺酸（以酸计）	Y=0.106 3X-0.040 3	2.31~115.59	0.999 7	0.012	0.023
4	二苯酮-4（以酸计）	Y=0.257 3X-0.012 7	1.20~59.86	1.000 0	0.004	0.012
5	亚苄基樟脑磺酸（以酸计）	Y=0.385 8X-0.037 2	1.36~67.85	0.999 9	0.004	0.014
8	樟脑苯扎铵甲基硫酸盐	Y=0.156 8X-0.016 0	1.13~56.58	0.999 8	0.011	0.011
23	二苯酮-2	Y=0.357 1X-0.088 7	1.04~20.89	0.999 3	0.003	0.021
3	二苯酮-3	Y=0.393 1X-0.111 5	1.96~97.83	0.999 8	0.006	0.020
1	3-亚苄基樟脑	Y=0.521 0X-0.089 6	0.60~30.17	0.999 5	0.006	0.018
17	对甲氧基肉桂酸异戊酯	Y=0.846 9X-0.090 3	2.07~103.32	0.999 9	0.004	0.010
2	4-甲基苄亚基樟脑	Y=0.777 4X-0.043 9	1.05~52.46	0.999 9	0.003	0.010
9	二乙氨羟苯甲酰基苯甲酸己酯	Y=0.083 7X+0.030 7	2.02~101.09	0.999 6	0.040	0.101
12	二甲基PABA乙基己酯	Y=0.883 2X-0.156 3	1.93~96.50	0.999 9	0.006	0.019
7	丁基甲氧基二苯甲酰基甲烷	Y=0.231 4X-0.102 7	1.22~61.14	0.999 3	0.024	0.061
19	奥克立林（以酸计）	Y=0.291 0X-0.133 3	2.19~109.50	0.999 8	0.015	0.045
13	甲氧基肉桂酸乙基己酯	Y=0.755 1X-0.251 8	1.99~99.66	0.999 7	0.006	0.060
14	水杨酸乙基己酯	Y=0.151 3X-0.009 7	2.46~122.92	1.000 0	0.012	0.049
16	胡莫柳酯	Y=0.160 8X+0.188 6	4.08~204.22	0.998 4	0.041	0.082
10	二乙基己基丁酰胺基三嗪酮	Y=1.249 2X-0.050 7	1.92~96.11	0.999 9	0.001	0.004
15	乙基己基三嗪酮	Y=1.313 3X-0.101 5	1.02~50.82	0.999 9	0.003	0.005
11	甲酚曲唑三硅氧烷	Y=0.156 8X-0.057 4	2.96~148.10	0.999 7	0.015	0.059
18	亚甲基双-苯并三唑基四甲基丁基酚	Y=0.441 2X-0.105 5	1.96~98.03	0.999 8	0.006	0.020
6	双-乙基己氧苯酚甲氧苯基三嗪	Y=0.648 9X-0.127 8	2.00~100.11	0.999 9	0.010	0.020

Tab. 3

Tab. 4

Recovery rate and relative standard deviation"

序号	对照品名称	加入量/μg	防晒霜		唇膏
序号	对照品名称	加入量/μg	平均回收率/%	RSD/%	平均回收率/%	RSD/%
20	苯基苯并咪唑磺酸（以酸计）	469.6	110.1	2.5	107.6	1.0
20	苯基苯并咪唑磺酸（以酸计）	2 348.0	106.3	2.1	104.2	2.3
22	对氨基苯甲酸	1 251.2	105.8	1.2	95.3	1.8
22	对氨基苯甲酸	6 256.1	88.3	3.4	89.6	2.3
21	对苯二亚甲基二樟脑磺酸（以酸计）	578.0	111.6	1.1	93.0	3.5
21	对苯二亚甲基二樟脑磺酸（以酸计）	2 889.8	108.5	1.2	91.1	91.1
4	二苯酮-4（以酸计）	299.3	99.8	0.9	91.3	0.7
4	二苯酮-4（以酸计）	1 496.6	98.1	3.7	89.1	1.7
5	亚苄基樟脑磺酸（以酸计）	339.3	110.3	1.8	109.2	1.1
5	亚苄基樟脑磺酸（以酸计）	1 696.3	113.2	1.9	107.2	4.7
8	樟脑苯扎铵甲基硫酸盐	282.9	94.8	4.6	94.4	2.0
8	樟脑苯扎铵甲基硫酸盐	1 414.5	93.4	3.7	91.4	1.6
23	二苯酮-2	261.1	111.6	2.7	110.2	3.4
23	二苯酮-2	1 305.5	93.6	1.9	95.6	2.8
3	二苯酮-3	489.2	108.7	2.5	106.8	2.2
3	二苯酮-3	2 445.8	108.8	4.5	100.1	1.6
1	3-亚苄基樟脑	150.8	100.3	0.7	103.9	3.1
1	3-亚苄基樟脑	754.2	100.1	4.5	105.1	4.1
17	对甲氧基肉桂酸异戊酯	516.6	109.7	3.7	112.6	1.2
17	对甲氧基肉桂酸异戊酯	2 583.1	108.2	4.4	110.2	1.8
2	4-甲基苄亚基樟脑	262.3	98.9	2.9	104.9	3.2
2	4-甲基苄亚基樟脑	1 311.5	97.8	4.9	101.2	2.0
9	二乙氨羟苯甲酰基苯甲酸己酯	505.4	110.2	3.8	98.8	3.3
9	二乙氨羟苯甲酰基苯甲酸己酯	2 527.2	105.0	3.0	104.7	1.6
12	二甲基PABA乙基己酯	482.5	107.3	2.0	102.2	2.6
12	二甲基PABA乙基己酯	2 412.5	99.8	2.8	99.1	0.8
7	丁基甲氧基二苯甲酰基甲烷	305.7	99.2	1.8	109.1	2.2
7	丁基甲氧基二苯甲酰基甲烷	1 528.5	100.2	3.3	100.9	2.3
19	奥克立林（以酸计）	547.4	105.5	2.9	106.8	3.2
19	奥克立林（以酸计）	2 737.2	101.6	4.0	106.5	2.0
13	甲氧基肉桂酸乙基己酯	498.3	100.0	4.5	106.5	2.7
13	甲氧基肉桂酸乙基己酯	2 491.5	100.1	3.1	103.8	1.9
14	水杨酸乙基己酯	614.6	96.4	0.5	93.6	3.5
14	水杨酸乙基己酯	3 073.0	90.8	3.7	90.9	5.4
16	胡莫柳酯	1 021.1	89.0	2.3	92.3	0.4
16	胡莫柳酯	5 105.6	93.3	3.9	87.9	0.8
10	二乙基己基丁酰胺基三嗪酮	480.6	85.6	0.4	87.4	1.9
10	二乙基己基丁酰胺基三嗪酮	2 402.8	87.6	1.3	86.2	1.2
15	乙基己基三嗪酮	254.1	89.8	1.5	99.8	3.3
15	乙基己基三嗪酮	1 270.6	86.6	2.0	95.6	1.5
11	甲酚曲唑三硅氧烷	740.5	106.4	3.7	100.1	1.8
11	甲酚曲唑三硅氧烷	3 702.4	109.0	2.3	108.0	4.7
18	亚甲基双-苯并三唑基四甲基丁基酚	490.2	98.3	4.9	101.5	3.9
18	亚甲基双-苯并三唑基四甲基丁基酚	2 450.8	93.1	3.0	97.1	1.6
6	双-乙基己氧苯酚甲氧苯基三嗪	500.5	89.2	2.2	101.3	4.6
6	双-乙基己氧苯酚甲氧苯基三嗪	2 502.7	86.4	1.3	99.2	1.5

Tab. 4

Tab. 5

序号	成分名称	检品编号
序号	成分名称	1	2	3	4	5	6	7
1	3-亚苄基樟脑
2	4-甲基苄亚基樟脑							√
3	二苯酮-3
4	二苯酮-4或二苯酮-5（以酸计）
5	亚苄基樟脑磺酸（以酸计）
6	双-乙基己氧苯酚甲氧苯基三嗪		√	×	√	√	√
7	丁基甲氧基二苯甲酰基甲烷	√						√
8	樟脑苯扎铵甲基硫酸盐
9	二乙氨羟苯甲酰基苯甲酸己酯		√	×		√	√
10	二乙基己基丁酰胺基三嗪酮
11	甲酚曲唑三硅氧烷
12	二甲基PABA乙基己酯
13	甲氧基肉桂酸乙基己酯	√		×	√	√	√	√
14	水杨酸乙基己酯		√		√
15	乙基己基三嗪酮		√	×			√
16	胡莫柳酯		√				√
17	对甲氧基肉桂酸异戊酯				√
18	亚甲基双-苯并三唑基四甲基丁基酚			×			√
19	奥克立林（以酸计）	√	√	×		√	√	√
20	苯基苯并咪唑磺酸（以酸计）			×		√
21	对苯二亚甲基二樟脑磺酸（以酸计）
22	对氨基苯甲酸
23	二苯酮-2

[1]	FDA. Sunscreen Drug Products for Over-the-Counter Human Use: Federal Register/Vol. 84, No.38/Tuesday, February 26, 2019/Proposed Rules: 6209.
[2]	The European Parliament and the Council of European Union. Regulation(EC) No 1223/2009 of the European Parliament and of the Council of 30 November 2009 on cosmetic products: Annex VI: List of UV Filters Allowed in Cosmetic Products. https://eur-lex.europa.eu/legal-content/EN/TXT/?qid=1415977955828&uri=CELEX:32009R1223.
[3]	[ The State Food and Drug Administration. Safety and Technical Standards for Cosmetics (2015 Edition) ] The State Food and Drug Administration. Safety and Technical Standards for Cosmetics (2015 Edition)[S]. Beijing: The State Food and Drug Administration, 2015.

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Simultaneous determination of 23 prohibited or restricted components in sunscreen cosmetics by high performance liquid chromatography

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t/min	φ（A）/%	φ（B）/%	φ（C）/%
0	18	2	80
4	6	25	69
8	25	45	30
16	25	45	30
20	20	40	40
22	45	50	5
25	50	45	5
28	18	2	80
40	18	2	80

序号	对照品名称	定容体积/mL	溶剂	取样量/mg
1	3-亚苄基樟脑	10	混合溶剂	31.10
2	4-甲基苄亚基樟脑	10	混合溶剂	52.55
3	二苯酮-3	25	混合溶剂	246.45
4	二苯酮-4	10	混合溶剂	60.53
5	亚苄基樟脑磺酸	10	混合溶剂	70.68
6	双-乙基己氧苯酚甲氧苯基三嗪	10	四氢呋喃	100.41
7	丁基甲氧基二苯甲酰基甲烷	10	四氢呋喃	62.31
8	樟脑苯扎铵甲基硫酸盐	5	混合溶剂	28.36
9	二乙氨羟苯甲酰基苯甲酸己酯	10	混合溶剂	101.19
10	二乙基己基丁酰胺基三嗪酮	10	四氢呋喃	98.88
11	甲酚曲唑三硅氧烷	5	四氢呋喃	75.56
12	二甲基PABA乙基己酯	10	混合溶剂	98.47
13	甲氧基肉桂酸乙基己酯	25	四氢呋喃	250.40
14	水杨酸乙基己酯	10	四氢呋喃	125.43
15	乙基己基三嗪酮	10	四氢呋喃	51.08
16	胡莫柳酯	10	四氢呋喃	205.25
17	对甲氧基肉桂酸异戊酯	10	混合溶剂	108.76
18	亚甲基双-苯并三唑基四甲基丁基酚	10	四氢呋喃	98.12
19	奥克立林	10	四氢呋喃	110.37
20	苯基苯并咪唑磺酸	10	50%四氢呋喃	100.34
21	对苯二亚甲基二樟脑磺酸	10	混合溶剂	116.76
22	对氨基苯甲酸	5	混合溶剂	126.77
23	二苯酮-2	5	混合溶剂	26.4

t/min	φ（A）/%	φ（B）/%	φ（C）/%
0	18	2	80
4	6	25	69
8	25	45	30
16	25	45	30
20	20	40	40
22	45	50	5
25	50	45	5
28	18	2	80
40	18	2	80

t/min	φ（A）/%	φ（B）/%	φ（C）/%
0	18	2	80
4	6	25	69
8	25	45	30
16	25	45	30
20	20	40	40
22	45	50	5
25	50	45	5
28	18	2	80
40	18	2	80