高效液相色谱法测定牙膏中防腐剂使用情况的研究

doi:10.3969/j.issn.2097-2806.2024.11.015

Abstract

Abstract:

Based on high performance liquid chromatography （HPLC） method under the item “Test Methods for Preservatives in Cosmetics” revised by the National Medical Products Administration Announcement No. 17 of 2021, the sample pretreatment condition was optimized, and 33 preservatives in 160 batches of toothpastes randomly selected from the market were tested. The detection results were subjected to multidimensional statistical analysis to understand the using status of preservatives in toothpastes, as well as the accuracy and authenticity of the labels, in order to accumulate data for the safety assessment and scientific supervision of preservatives in toothpastes. The results show that the optimized pretreatment condition is suitable for the extraction of preservatives from toothpastes, and the recovery rate is good. The samples produced from Guangdong and Jiangsu provinces are the most, accounting for 54% of the total samples. A total of 13 preservatives are detected in 160 batches of toothpastes, among which benzoic acid and its sodium salt has the highest detection rate, reaching 35.0%. The amount of preservatives added in different toothpastes varies greatly. The highest detected value is benzoic acid and its sodium salt, with a content of 0.44%; and the lowest detected value is 4-hydroxybenzoic acid and its sodium salt, with a content of only 0.000 57%. One type of the preservatives is detected in 38.1% of the samples, while two or more types of preservatives are detected in 34.4% of the samples. The detection results of 61 batches of the toothpastes are inconsistent with the labels, among which the majority of the preservatives not indicated on labels are detected, that will pose certain safety risks. It is recommended to pay continuous attention to the quality and safety of toothpastes in the future work, strengthen the supervision of toothpastes, and urge enterprises to standardize production.

Key words: toothpaste, preservative, high performance liquid chromatography, result analysis, supervision suggestion

CLC Number:

TQ658

Liangyu Zhang, Haiying Yu, Silong Li, Yaqi Jiang, Weijian Wang, Qiyan Li, Junjie Li. Study on the using status of preservatives in toothpastes based on HPLC[J].China Surfactant Detergent & Cosmetics, 2024, 54(11): 1397-1404.

Figures/Tables 12

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References 9

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序号	分组	组分名称	检测波长/nm	序号	分组	组分名称	检测波长/nm
1	第一组	甲基异噻唑啉酮	280	1	第二组	水杨酸	280
2		甲基氯异噻唑啉酮	280	2		山梨酸	280
3		苯氧乙醇	280	3		苯氧异丙醇	280
4		脱氢乙酸	280	4		邻伞花烃-5-醇	280
5		4-羟基苯甲酸	254	5		氯二甲酚	280
6		苯甲醇	254	6		三氯卡班	280
7		4-羟基苯甲酸甲酯	254	7		三氯生	280
8		4-羟基苯甲酸乙酯	254	8		碘丙炔醇丁基氨甲酸酯	230
9		4-羟基苯甲酸异丙酯	254	9		对氯间甲酚	230
10		4-羟基苯甲酸丙酯	254	10		2, 4-二氯苯甲醇	230
11		4-羟基苯甲酸苯酯	254	11		邻苯基苯酚	230
12		4-羟基苯甲酸异丁酯	254	12		氯咪巴唑	230
13		4-羟基苯甲酸丁酯	254	13		吡罗克酮乙醇胺盐	230
14		4-羟基苯甲酸苄酯	254	14		溴氯芬	230
15		4-羟基苯甲酸戊酯	254
16		2-溴-2-硝基丙烷-1, 3-二醇	230
17		苯甲酸	230
18		氯苯甘醚	230
19		5-溴-5-硝基-1, 3-二噁烷	230

时间/min	φ（A）/%	φ（B）/%
0	90	10
5.0	90	10
29.0	50	50
41.0	65	35
52.0	35	65
55.0	90	10
60.0	90	10

时间/min	φ（A）/%	φ（B）/%
0	80	20
5.0	55	45
15.0	55	45
32.0	30	70
47.0	15	85
54.0	15	85
55.0	55	45
60.0	55	45
60.1	80	20
65.0	80	20

前处理方式	测得含量/（μg/g）
前处理方式	苯甲酸	苯甲醇	苯氧乙醇
水	551	273	519
0.1%磷酸水	559	280	528
水+石英砂	586	308	552
0.1%磷酸水+氯化钠	574	295	541
0.1%磷酸水+石英砂	598	312	563

序号	组分名称	检出批次/批	检出率/%
1	苯甲酸及其钠盐	56	35.0
2	苯甲醇	43	26.9
3	4-羟基苯甲酸甲酯及其钠盐	29	18.1
4	4-羟基苯甲酸及其钠盐	22	13.8
5	4-羟基苯甲酸丙酯及其钠盐	17	10.6
6	水杨酸及其钠盐	15	9.4
7	4-羟基苯甲酸乙酯及其钠盐	7	4.4
8	三氯生	6	3.8
9	邻伞花烃-5-醇	2	1.3
10	4-羟基苯甲酸丁酯及其钠盐	1	0.6
11	苯氧乙醇	1	0.6
12	脱氢乙酸	1	0.6
13	山梨酸及其盐类	1	0.6

Study on the using status of preservatives in toothpastes based on HPLC

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序号	组分名称	限值/%		最大值/%	最小值/%	平均值/%	中位值/%
序号	组分名称	《牙膏用原料规范》（GB 22115—2008）	《化妆品安全技术规范》（2015年版）	最大值/%	最小值/%	平均值/%	中位值/%
1	苯甲酸及其钠盐	≤0.5（以酸计）	≤0.5（以酸计）	0.44	0.000 82	0.13	0.11
2	苯甲醇	≤1.0	≤1.0	0.22	0.009 4	0.060	0.031
3	4-羟基苯甲酸甲酯及其钠盐	≤0.4（以酸计）	≤0.4（以酸计）	0.19	0.002 3	0.058	0.048
4	4-羟基苯甲酸及其钠盐	≤0.4（以酸计）	≤0.4（以酸计）	0.038	0.000 57	0.006 3	0.003 5
5	4-羟基苯甲酸丙酯及其钠盐	≤0.4（以酸计）	≤0.14（以酸计）	0.098	0.001 0	0.046	0.045
6	水杨酸及其钠盐	≤0.5（以酸计）	≤0.5（以酸计）	0.16	0.006 2	0.031	0.024
7	4-羟基苯甲酸乙酯及其钠盐	≤0.4（以酸计）	≤0.4（以酸计）	0.06	0.000 88	0.029	0.024
8	三氯生	≤0.3	不得添加	0.054	0.019	0.034	0.031
9	邻伞花烃-5-醇	≤0.1	≤0.1	0.035	0.016	0.026	0.026
10	4-羟基苯甲酸丁酯及其钠盐	≤0.4（以酸计）	≤0.14（以酸计）	0.041	0.041	0.041	0.041
11	苯氧乙醇	≤1.0	≤1.0	0.11	0.11	0.11	0.11
12	脱氢乙酸	≤0.6（以酸计）	≤0.6（以酸计）	0.000 82	0.000 82	0.000 82	0.000 82
13	山梨酸及其盐类	≤0.6（以酸计）	≤0.6（以酸计）	0.000 99	0.000 99	0.000 99	0.000 99

检出组分种类	批数/批	所占比例/%
0种	44	27.5
1种	61	38.1
2种	36	22.5
3种	12	7.5
4种	5	3.1
5种	1	0.6
6种	1	0.6
总计	160	100.0

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