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

Abstract

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

CLC Number:

TQ658.3 +4

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.

Figures/Tables 4

Tab. 1

Tab. 2

Tab. 3

Determination of permitted hair dyes by HPLC method"

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

Tab. 3

Tab. 4

References 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

Research progress on detection and application of permitted hair dyes in hair-dyeing cosmetics

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