染发产品中准用染发剂的检测方法和使用情况研究进展

doi:10.3969/j.issn.1001-1803.2019.07.007

摘要/Abstract

摘要：

概述了染发产品的种类、安全风险和《化妆品安全技术规范》（2015年版）对准用染发剂的规定,介绍目前检测标准和文献方法所涵盖的准用染发剂范围,综述了液相色谱、液相色谱-质谱、气相色谱、气相色谱-质谱等方法在染发剂测定上的应用情况及其优劣,并对近年来国内市场上染发产品中准用染发剂的使用情况进行了分析,最后提出了染发剂检测技术的发展趋势。

关键词: 染发产品, 染发剂, 检测, 使用, 进展

Abstract:

The categories and safety risks of hair-dyeing cosmetics, and the provision of permitted hair dyes in “Cosmetics Safety Technical Specifications”（2015 Edition）were presented. The detection standards and cutting-edge report methods referring the specific hair dyes which were legally permitted in the hair-dying products were introduced. The advantages and disadvantages of various detection methods were introduced, including HPLC, HPLC-MS, GC, GC-MS and etc. The article focused on the usage of permitted hair dyes in hair-dyeing cosmetics in the domestic market in recent year. Finally, the development trend of hair dye detection methods was proposed.

Key words: hair-dyeing cosmetics, hair dyes, detection, application, progress

中图分类号:

TQ658.3 +4

顾宇翔,郑翌,顾澄皓. 染发产品中准用染发剂的检测方法和使用情况研究进展[J]. 日用化学工业, 2019, 49(7): 456-463.

GU Yu-xiang,ZHENG Yi,GU Cheng-hao. Research progress on detection and application of permitted hair dyes in hair-dyeing cosmetics[J]. China Surfactant Detergent & Cosmetics, 2019, 49(7): 456-463.

图/表 4

表 1

表 2

表 3

液相色谱法检测准用染发剂"

标准	提取溶剂	色谱柱	检测波长/nm	流动相	检出限/（mg·kg^-1）	回收率/%
GB/T 24800.12—2009（液相色谱法）	2 g样品于50 mL具塞比色管,加入1 mL 2%亚硫酸钠溶液、25 mL甲醇,漩涡振荡30 s,再加入15 mL甲醇,混匀,超声15 min,甲醇定容	C₁₈（250 mm× 4.6 mm,5 μm）	280	V（pH=7.7三乙醇胺磷酸缓冲溶液）∶V（乙腈）=97∶3,1 mL/min	150	73~102
GB/T 35824—2018	（方法一）1 g样品于25 mL具塞刻度塑料离心管中,加入10 mL甲醇涡旋并超声10 min,用甲醇定容至25 mL,涡旋混合,超声10 min, 5 000 r/min离心10 min。移取上层提取液5 mL于5 mL刻度塑料试管中,氮吹浓缩至约0.5 mL,然后用V（乙醇）∶V（50 mmol/L磷酸盐缓冲液）=5∶95定容至5 mL,涡旋1 min。（方法二）1 g样品于25 mL具塞刻度塑料离心管中,加入V（乙醇）∶V（50 mmol/L磷酸盐缓冲液）=1∶1混合溶液定容至25 mL,涡旋 1 min,超声15 min,5 000 r/min离心10 min,取上清液	Poroshell HPH C₁₈（100 mm× 3.0 mm,2.7 μm）	225,280	50 mmol/L磷酸盐缓冲液溶液（含3%甲醇）-甲醇梯度洗脱,0.5 mL/min	15~60	80.3~115.0
化妆品安全技术规范（对苯二胺等8种物质）	样品0.5 g于已加入1%亚硫酸钠溶液1 mL的25 mL具塞比色管中,加50%乙醇溶液至刻度,超声提取 15 min,离心取上清液	C₁₈（250 mm× 4.6 mm,10 μm）	280	V（pH=7.7三乙醇胺磷酸缓冲溶液）∶V（乙腈）= 95∶5,2 mL/min	150~800
化妆品安全技术规范（对苯二胺等32种物质）	样品0.5 g于10 mL具塞比色管中,加50 %乙醇溶液至刻度,涡旋 1 min,冰浴超声15 min。如为浑浊溶液,可取适量离心（5 000 r/min）5 min,取上清液	RP-AMIDE C₁₈柱（250 mm × 4.6 mm,5 μm）	280	（1）V（乙腈）∶V（磷酸盐混合溶液= 1∶9,（2）V（甲醇）∶V（磷酸盐混合溶液=）1∶9,（3）V（乙腈）∶V（磷酸盐混合溶液）=4∶6,1 mL/min	10~100	86~114
化妆品安全技术规范（碱性橙31等7种物质）	称取样品5 g于25 mL具塞比色管中,加入1 mL四氢呋喃,再加入20 mL甲醇,涡旋振荡2 min,超声提取30 min,冷却至室温,甲醇定容	C₁₈（250 mm× 4.6 mm,5 μm）	480,520,616	甲醇-0.02 mol/L乙酸铵（pH=4）梯度洗脱,1 mL/min	0.06~3.0	85.2~109.2
文献[13]	1 g样品于25 mL具塞刻度塑料离心管中,加入10 mL甲醇,涡旋并超声10 min,甲醇定容,超声提取 10 min,5 000 r/min 离心10 min。移取上层提取液5 mL于5 mL塑料试管中,氮吹浓缩至约0.5 mL,用 V（乙醇）∶V（50 mmol/L磷酸盐缓冲液）=5∶95溶液定容至5 mL,涡旋1 min,取上清液	Agilent Poroshell HPH C₁₈（100 mm× 3.0 mm,2.7 μm）	225,280	50 mmol/L磷酸盐缓冲液溶液（含3%甲醇）-甲醇梯度洗脱,0.5 mL/min	15~60	80.3~115.0
文献[14]	试样1 g于50 mL具塞离心管中,加入20 mL甲醇,旋涡混匀1 min,冰浴超声15 min,4 ℃以10 000 r/min离心5 min	XB-C₁₈（250 mm× 4.6 mm,5 μm）	240,270,410,450	乙腈-0.02 mol/L乙酸铵溶液梯度洗脱,1 mL/min	0.35~2.5	85.4~99.9
文献[17]	0.5 g样品于50 mL离心管中,加入10 mL甲醇,旋涡混匀2 min,冰浴超声15 min,取上清液	XB-C₁₈（250 mm× 4.6 mm,5 μm）	420,490,540,600	乙腈-0.02 mol/L乙酸铵（含0.05%甲酸）梯度洗脱, 1 mL/min	0.2~0.6	93.9~102.5

表 3

表 4

参考文献 29

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序号	名称	INCI名	化妆品安全技术规范	国标、行标
1	1,5-萘二酚（CI 76625）	1,5-Naphthalenediol	√
2	1-萘酚（CI 76605）	1-Naphthol	√
3	2,4-二氨基苯氧基乙醇盐酸盐	2,4-Diaminophenoxyethanol HCl	√
4	2,6-二氨基吡啶	2,6-Diaminopyridine	√
5	2,7-萘二酚（CI 76645）	2,7-Naphthale nediol	√
6	2-氨基-3-羟基吡啶	2-Amino-3-hydroxypyridine	√
7	2-氯对苯二胺硫酸盐	2-Chloro-p-phenylenediamine sulfate	√	√
8	2-甲基间苯二酚	2-Methylresorcinol	√	√
9	4-氨基-2-羟基甲苯	4-Amino-2-hydroxytoluene	√	√
10	4-氨基-3-硝基苯酚	4-Amino-3-nitrophenol	√	√
11	4-氨基间甲酚	4-Amino-m-cresol	√
12	4-氯间苯二酚	4-Chlororesorcinol	√
13	4-硝基邻苯二胺	4-Nitro-o-phenylenediamine	√
14	6-氨基间甲酚	6-Amino-m-cresol	√	√
15	6-羟基吲哚	6-Hydroxyindole	√
16	酸性紫43号（CI 60730）	Acid Violet 43	√
17	碱性橙31号	Basic orange 31	√
18	碱性红51号	Basic red 51	√
19	碱性黄87号	Basic yellow 87	√
20	间氨基苯酚	m-Aminophenol	√	√
21	N,N-双（2-羟乙基）对苯二胺硫酸盐	N,N-Bis（2-hydroxyethyl）-p-phenylenediamine sulfate	√
22	N-苯基对苯二胺（CI 76085）	N-phenyl-p-phenylenediamine	√
23	对氨基苯酚	p-Aminophenol	√	√
24	苯基甲基吡唑啉酮	Phenyl methyl pyrazolone	√
25	对甲基氨基苯酚	p-Methylaminophenol	√
26	对甲基氨基苯酚硫酸盐	p-Methylaminophenol sulfate	√	√
27	对苯二胺	p-Phenylenediamine	√	√
28	间苯二酚	Resorcinol	√	√
29	甲苯-2,5-二胺	Toluene-2,5-diamine	√
30	甲苯-2,5-二胺硫酸盐	Toluene-2,5-diamine sulfate	√	√

序号	名称	文献[12]	文献[13]	文献[14]	文献[15]	文献[16]	文献[17]	文献[18]
1	1-羟乙基- 4,5-二氨基吡唑硫酸盐					√
2	2,6-二羟乙基氨甲苯				√
3	2,6-二甲氧基-3,5-吡啶二胺盐酸盐				√
4	2-甲基-5-羟乙氨基苯酚		√		√
5	3-硝基对羟乙氨基酚				√
6	5-氨基-6-氯-邻甲酚		√		√
7	6-甲氧基-2-甲氨基-3-氨基吡啶盐酸盐（HC蓝7号）			√
8	碱性红76号（CI 12245）						√
9	分散黑9号			√
10	分散紫1号			√
11	HC橙1号			√
12	HC红1号			√
13	HC红3号			√
14	HC黄2号			√
15	HC黄4号			√
16	羟苯并吗啉		√
17	羟乙基-2-硝基对甲苯胺				√
18	羟乙基-3,4-亚甲二氧基苯胺盐酸盐					√
19	苦氨酸钠	√
20	四氨基嘧啶硫酸盐							√

文献	提取净化方法	色谱柱	流动相	质谱模式	检出限/（mg·kg^-1）	回收率/%
[15]	试样0.5 g于50 mL具塞比色管内,加入40 mL 甲醇,涡旋混匀1 min后超声提取15 min,甲醇定容,10 000 r/min 离心5 min,取上清液	Waters BEH C₁₈（100 mm×2.1 mm,1.7 μm）	10 mmol/L乙酸铵-乙腈梯度洗脱,0.3 mL/min	ESI正离子	0.034~7	90~110
[16]	试样0.5 g于50 mL 具塞比色管内,加入40 mL水,涡旋混匀1 min后超声提取15 min,用水定容, 10 000 r/min 离心5 min,取上清液	Waters Acquity UPLC BEH C₁₈（100 mm×2.1 mm,1.7 μm）	10 mmol/L乙酸铵-乙腈梯度洗脱,0.3 mL/min	ESI正离子	0.42~4.6	83.0~92.2
[18]	试样0.5 g于50 mL具塞比色管内,加入40 mL 0.3%甲酸,涡旋混匀1 min后超声提取15 min,0.3%甲酸定容,10 000 r/min离心5 min,取上清液	Waters Acquity UPLC BEH C₁₈（100 mm×2.1 mm,1.7 μm）	10 mmol/L乙酸铵-乙腈梯度洗脱,0.3 mL/min	ESI正离子	0.17	87.5~96.0