CN105769596B - A kind of hair dyeing synergist and its preparation and application - Google Patents
A kind of hair dyeing synergist and its preparation and application Download PDFInfo
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Abstract
The invention belongs to cosmetics industry technical field, specifically a kind of hair dyeing synergist and its preparation and application.Synergist is as shown in Equation 1, and the synergist is used in hair dye, as hair dyeing synergist.The synergist of dyeing formulation of the present invention, compound structure are novel, and synthesis technology is simple, in conjunction with dyestuff and can have the function of opening hair scale piece as synergist, dye molecule is brought into inside hair scale piece, the colouring power of dyestuff is increased.Its application range is not limited to a certain dyestuff, and can be widely used for mixture in all kinds of type dyes is hair dye.
Description
Technical field
The invention belongs to cosmetics industry technical field, specifically a kind of hair dyeing synergist and its preparation and application.
Background technique
With the continuous improvement of people's living standards, appearance is increasingly valued by the people, many young men are in order to pursue
In order to cover white hair, hair dye has become cosmetic product indispensable in people's life by fashion, the elderly.At present on the market
There is a large amount of hair dye, but according to detection, most of hair dye contains the chemicals being harmful to the human body, such as：It is oxidant, right
Phenylenediamine etc..It is reported that hair dye has become a major incentive for causing contact dermatitis, in contact dermatitis patient
In, its disease of 20% people is due to caused by hair dyeing, and Long Term Contact is it is also possible to induce the pernicious diseases such as leukaemia, cutaneum carcinoma
Disease, therefore hair dyeing has become a serious social concern.
To solve the above-mentioned problems, many major companies both domestic and external successively have developed various types of non-p-phenylenediamine class dyes
Agent is sent out, the synergistic effect of dyestuff and synergist is all made of, hair is dyed, but all there is dyeing time length, fastness to washing
The disadvantages of difference (washing 8 times to fade substantially very seriously) and easy pollution skin and scalp.
Due to the unique hair scale chip architecture of hair surface, hair is dyed relatively to cotton, wool dyeing using dyestuff
It is difficult.In order to enable dyestuff preferably to enter inside hair, using thioacetic acid and cysteine, (structural formula is as follows for Pei La company
It is shown) etc. the reagent containing sulfydryl and hair act on, the hair scale piece of hair surface can be opened, tie dyestuff preferably with hair
It closes, promotes dyeing effect, but unfortunately, due to thioacetic acid and cysteine have offensive odour, so that formula
There is certain obstruction in application aspect.
In view of the above problems, need to invent a kind of hair dye synergist, it can be with most of dyestuff compatibilities, nothing safe to the human body
Evil is without sensitization phenomenon, and hair feel is smooth after dyeing, invariably euosmia, and utilizes hair dye formulas energy made from the synergist
Achieve the effect that permanent hair dye in the market.
Summary of the invention
It is an object of that present invention to provide a kind of synergist of the structure novel of hair dyeing and its preparations and application.
To achieve the above object, the invention adopts a technical scheme as：
A kind of hair dyeing synergist, synergist is as shown in Equation 1,
A kind of preparation method for synergist of having hair dyed,
Reaction equation is as follows
1) chloracetyl chloride reacts under -10-50 DEG C, pH value=2-10 system under acid binding agent effect with cysteine sodium
0.5-3h generates 2- (2- chloracetyl amido) -3- mercaptopropionic acid sodium；Wherein, chloracetyl chloride and cysteine sodium, acid binding agent rub
You are than being 1~1.5:1:0.5~1.2；
2) 2- (2- chloracetyl amido) -3- mercaptopropionic acid of above-mentioned acquisition reacts 1-30h generation with thiocarbamide at 0-100 DEG C
2- [2- (carbonamidine sulfydryl) acetamido] -3- mercaptopropionic acid；Wherein, 2- (2- chloroethene acid imide) -3- mercaptopropionic acid and thiocarbamide
Molar ratio is 1:1~2；
3) 2- of above-mentioned acquisition [2- (carbonamidine sulfydryl) acetamido] -3- mercaptopropionic acid is hydrolyzed obtain under alkaline condition
Synergist 2- shown in formula 1 [2- (sulfydryl) acetamido] -3- mercaptopropionic acid.
Synergist preparation method is preferably,
1) chloracetyl chloride reacts under -5-10 DEG C, pH value=6-8 system under acid binding agent effect with cysteine sodium
1.5-2.5h generates 2- (2- chloracetyl amido) -3- mercaptopropionic acid sodium；Wherein, chloracetyl chloride and cysteine sodium, acid binding agent
Molar ratio is 1~1.2:1:0.5~0.8；
2) it is raw to react 10-12h with thiocarbamide at 10-40 DEG C for 2- (2- chloracetyl amido) -3- mercaptopropionic acid of above-mentioned acquisition
At 2- [2- (carbonamidine sulfydryl) acetamido] -3- mercaptopropionic acid；Wherein, 2- (2- chloroethene acid imide) -3- mercaptopropionic acid and thiocarbamide
Molar ratio be 1:1-1.5；
3) 2- of above-mentioned acquisition [2- (carbonamidine sulfydryl) acetamido] -3- mercaptopropionic acid is hydrolyzed obtain under alkaline condition
Synergist 2- shown in formula 1 [2- (sulfydryl) acetamido] -3- mercaptopropionic acid.
The hydrolyst of the hydrolyzed under basic conditions is alkali or alkaline earth metal.
The hydrolyst is hydroxide.
The hydrolyst is barium hydroxide.
A kind of application for synergist of having hair dyed, the synergist is used in hair dye, as hair dyeing synergist.The hair dye
Keratoprotein can be dyed, such as nail, beard, eyebrow etc..
When the preparation hair dye using above-mentioned synergist, mixture can be carried out according to existing hair dye ingredient, specially：
Dyestuff is selected from the dyestuff that may be used as cosmetics coloring and food color of European Union's approval, such as：Solvent dye, acidity
One of dyestuff, basic dye, direct dyes, pigment or a variety of mixing.
Hair swelling agent can be improved dyeability, wherein signified swelling agent can be known to the art such as benzene
Methanol, urea, lauryl sodium sulfate, glucose, sucrose.
Thickener can be the thickener for ratifying in terms of cosmetics.Such as oleic acid, hexadecanol, octadecyl alcolol, oleyl alcohol, Ka Boshu
One or more of rouge, xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose.
Alkaline agent can be such that hair softens, and alkaline agent includes one or more of composition：Ornithine, arginine, lysine, ammonia
Water, monoethanolamine, diethanol amine, triethanolamine, alkylolamides, hydroxide, hydroxide such as sodium hydroxide or contain carbonic acid
Salt, carbonate containing such as sodium carbonate etc..
Advantage for present invention：
The synergist of dyeing formulation of the present invention, compound structure are novel, and synthesis technology is simple, can be with as synergist
Dyestuff combines and has the function of opening hair scale piece, and dye molecule is brought into inside hair scale piece, the colouring power of dyestuff is increased.Its
Application range is not limited to a certain dyestuff, and can be widely used for mixture in all kinds of type dyes is hair dye.
Synergist of the present invention can be beaten containing can have both there are two sulfydryl in synergist compound with a plurality of types of dyestuff compatibilities
The function of wool opening scale can enable dye molecule be easier to enter inside hair, preferably in conjunction with hair.Hair dye is obtained to match
Square staining power is good, does not damage to hair；Hair after dyeing washs 30 front and back nothings by normal hair washing method and obviously falls
Color phenomenon.Synergist of the present invention is different from other mercapto reagents, and odorless, tasteless is avoided and generated not in traditional hair dye
Euosmia.Synergist of the present invention can with most of dyestuff compatibilities, using the hair dye formulas compounded by the synergist to hair
It is dyed, harmless no sensitization phenomenon safe to the human body, hair feel is smooth after dyeing, invariably euosmia, can generate permanent
The hair dyeing effect of property.
Specific embodiment
Example is used to further illustrate the present invention in detail below, but the present invention is limited to absolutely not these examples.
Synergist synthetic example
Embodiment 1
At room temperature, 14.3g (0.1mol) cysteine sodium is dissolved in 100ml water, with ice-water bath be cooled to 0 DEG C with
Under, 12.4g (0.11mol) chloracetyl chloride is added dropwise, while the 30ml sodium carbonate liquor that mass fraction is 17.6% is added dropwise
(0.05mol) maintains pH between 7-8, time for adding 30min or so, and reaction 3h is stirred for after being added dropwise, is then warming up to
Room temperature is gradually added thiocarbamide 7.6g (0.1mol), and 10min addition finishes, and continues to stir 12h, by the white solid powder of precipitation
Filtering, and with 100ml water washing, it is dried to obtain 21.2g 2- [2- (ghiourea group) acetamido] -3- mercaptopropionic acid, yield
89.4%.1H-NMR(400MHz,CDCl3)δ:1.5(1H,s),2.93-3.18(2H,m),3.76(2H,m),4.78(1H,m),
8.32(1H,s),9.27-9.29(3H,m),12.57(1H,s)。
23.6g (0.1mol) 2- [2- (ghiourea group) acetamido] -3- mercaptopropionic acid is weighed, adds water 200ml, and hydrogen is added
Barium monoxide 17.1g (0.1mol), is heated to 50-60 DEG C, hydrolyzes 3h, after in 70 DEG C of vacuum distillations remove water, obtain consolidating shown in formula 1
Body 2- [2- (sulfydryl) acetamido] -3- mercaptopropionic acid 18.8g (yield 90%), 1H-NMR (400MHz, CDCl3),δ:1.5
(1H,s),1.7(1H,s),2.0(1H,s),2.79-3.04(2H,m),3.71(2H,m),3.72(2H,m),3.81(3H,m),
11.0(1H,s)。
Embodiment 2
143g (1mol) cysteine sodium is dissolved in 1L water, 0-5 DEG C is cooled to ice-water bath, is added dropwise 271g (1.2mol)
Chloracetyl chloride, while the 300ml sodium carbonate liquor (0.5mol) that mass fraction is 17.6% is added dropwise, maintain pH between 7-8, drop
5h or so between added-time is stirred for reaction 3h, is then warming up to room temperature, is gradually added thiocarbamide 91.2g (1.2mol) after being added dropwise,
2h addition finishes, and continues to stir 12h, the white solid powder of precipitation is filtered, and with 1L water washing, is dried to obtain 215.7g
2- [2- (ghiourea group) acetamido] -3- mercaptopropionic acid, yield 91%.1H-NMR(400MHz,CDCl3)δ:1.5(1H,s),
2.93-3.18(2H,m),3.76(2H,m),4.78(1H,m),8.32(1H,s),9.27-9.29(3H,m),12.57(1H,s)。
236g (1mol) 2- [2- (ghiourea group) acetamido] -3- mercaptopropionic acid is weighed, adds water 2L, and barium hydroxide is added
171g (1mol), is heated to 60-70 DEG C, hydrolyzes 4h, after in 70 DEG C of vacuum distillations removing water, obtain solid 2- [2- shown in formula 1
(sulfydryl) acetamido] -3- mercaptopropionic acid 173g (yield 89%), 1H-NMR (400MHz, CDCl3),δ:1.5(1H,s),1.7
(1H,s),2.0(1H,s),2.79-3.04(2H,m),3.71(2H,m),3.72(2H,m),3.81(3H,m),11.0(1H,s)。
Hair dye formulas embodiment：
Involved in following hair dyes in addition to synergist, all reagents derive from commercially available.
Embodiment 1：
Synergist and dyestuff etc. are made into formula (referring to table 1) according to following table, that is, obtain corresponding hair dye.
Table 1
Embodiment 2：
Synergist and dyestuff etc. are made into formula (referring to table 2) according to following table, that is, obtain corresponding hair dye.
Table 2
Embodiment 3：
Synergist and dyestuff etc. are made into formula (referring to table 3) according to following table, that is, obtain corresponding hair dye.
Table 3
Comparative example 1
By configuration hair dye (referring to table 4) is recorded in following tables, that is, obtain corresponding hair dye.
Table 4
Comparative example 2
By configuration hair dye (referring to table 5) is recorded in following tables, that is, obtain corresponding hair dye.
Table 5
The hair dye point obtained in the hair dye and comparative example that above-mentioned hair dye preparation embodiment obtains is dipped with hairbrush
Be not applied to 100% it is greyish white deliver face, have hair dyed 15~30min as needed at 20~30 DEG C, after cleaned with warm water.
Hair swatch is washed using the shampoo containing 1% hydrogen peroxide, washes rear naturally dry.
PERFORMANCE EXAMPLES：
Embodiment 1
After taking the hair dye obtained using above-mentioned hair dye preparation embodiment and the hair dye dye obtained in comparative example
Hair swatch is washed 30 times by normal hair washing program, the colouring discrimination of washing front and back is measured using colour photometer, indicates color with Δ E
Difference.
Hair in table 1 after formula dyeing, Δ E1=0.2
Hair in table 2 after formula dyeing, Δ E2=0.1
Hair in table 3 after formula dyeing, Δ E3=0.6
Hair in table 4 after formula dyeing, Δ E3=3.5
Hair in table 5 after formula dyeing, Δ E3=6.2
Δ E < 1 illustrates that washing front and back substantially without discolouration phenomena, illustrates using synergist effect of the invention better than similar increasing
Imitate agent.
The standard of permanent type hair dye in the market can be reached using the hair dye fastness to washing that synergist of the present invention obtains.
The hair dyeing obtained in the hair dye and comparative example that above-mentioned hair dye preparation embodiment obtains is irradiated with xenon lamp respectively
Hair swatch after agent dyeing, temperature set 60 DEG C, and radiation intensity sets 0.65W/M2, wavelength 340nm, and defeated in specification
Frequency spectrum ultraviolet ray intensity 1.4W/M2 wavelength 420nm is suitable out, and test period is for 24 hours (positive 12h, reverse side 12h).
The colouring discrimination that irradiation front and back is measured using colour photometer, indicates value of chromatism with Δ E.
Hair in table 1 after formula dyeing, Δ E1=0.3
Hair in table 2 after formula dyeing, Δ E2=0.1
Hair in table 3 after formula dyeing, Δ E3=0.5
Hair in table 4 after formula dyeing, Δ E3=2.4
Hair in table 5 after formula dyeing, Δ E3=3.1
Δ E < 1 illustrates that xenon lamp irradiation front and back substantially without discolouration phenomena, illustrates using synergist effect of the invention better than same
Class synergist.
Claims (5)
1. a kind of preparation method for synergist of having hair dyed, it is characterised in that：
Reaction equation is as follows
1) chloracetyl chloride reacts 0.5- under -10-50 DEG C, pH value=2-10 system under acid binding agent effect with cysteine sodium
3h generates 2- (2- chloracetyl amido) -3- mercaptopropionic acid sodium；Wherein, the molar ratio of chloracetyl chloride and cysteine sodium, acid binding agent
It is 1~1.5:1:0.5~1.2；
2) 2- (2- chloracetyl amido) -3- mercaptopropionic acid of above-mentioned acquisition reacts 1-30h generation 2- with thiocarbamide at 0-100 DEG C
[2- (carbonamidine sulfydryl) acetamido] -3- mercaptopropionic acid；Wherein, 2- (2- chloroethene acid imide) -3- mercaptopropionic acid and thiocarbamide rub
You are than being 1:1~2；
3) 2- of above-mentioned acquisition [2- (carbonamidine sulfydryl) acetamido] -3- mercaptopropionic acid is hydrolyzed obtain synergy under alkaline condition
Agent 2- [2- (sulfydryl) acetamido] -3- mercaptopropionic acid.
2. the preparation method of hair dyeing synergist according to claim 1, it is characterised in that：
1) chloracetyl chloride reacts 1.5- under -5-10 DEG C, pH value=6-8 system under acid binding agent effect with cysteine sodium
2.5h generates 2- (2- chloracetyl amido) -3- mercaptopropionic acid sodium；Wherein, mole of chloracetyl chloride and cysteine sodium, acid binding agent
Than being 1~1.2:1:0.5~0.8；
2) 2- (2- chloracetyl amido) -3- mercaptopropionic acid of above-mentioned acquisition reacts 10-12h generation 2- with thiocarbamide at 10-40 DEG C
[2- (carbonamidine sulfydryl) acetamido] -3- mercaptopropionic acid；Wherein, 2- (2- chloroethene acid imide) -3- mercaptopropionic acid and thiocarbamide rub
You are than being 1:1-1.5；
3) 2- of above-mentioned acquisition [2- (carbonamidine sulfydryl) acetamido] -3- mercaptopropionic acid is hydrolyzed obtain synergy under alkaline condition
Agent 2- [2- (sulfydryl) acetamido] -3- mercaptopropionic acid.
3. the preparation method of hair dyeing synergist as described in claim 1 or 2, it is characterised in that：The hydrolyzed under basic conditions
Hydrolyst be alkali or alkaline earth metal.
4. the preparation method of hair dyeing synergist according to claim 3, it is characterised in that：The hydrolyst is hydroxide
Object.
5. the preparation method of hair dyeing synergist according to claim 4, it is characterised in that：The hydrolyst is hydroxide
Barium.
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|---|---|---|---|---|
| CN1401310A (en) * | 2001-08-15 | 2003-03-12 | 王明彰 | Use of DL-cystine, DL-cysteine and their salt in dyeing and perming hair |
| CN1679488A (en) * | 2004-04-06 | 2005-10-12 | 欧莱雅 | Use of dimercaptoamides for permanently deforming of keratinic fibres |
| CN103068930A (en) * | 2010-08-17 | 2013-04-24 | 巴斯夫欧洲公司 | Disulfide or thiol polymeric hair dyes |
-
2014
- 2014-12-15 CN CN201410775944.6A patent/CN105769596B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401310A (en) * | 2001-08-15 | 2003-03-12 | 王明彰 | Use of DL-cystine, DL-cysteine and their salt in dyeing and perming hair |
| CN1679488A (en) * | 2004-04-06 | 2005-10-12 | 欧莱雅 | Use of dimercaptoamides for permanently deforming of keratinic fibres |
| CN103068930A (en) * | 2010-08-17 | 2013-04-24 | 巴斯夫欧洲公司 | Disulfide or thiol polymeric hair dyes |
Non-Patent Citations (3)
| Title |
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| Improved Electron-Conformational Method of Pharmacophore Identification and Bioactivity Prediction. Application to Angiotensin Converting Enzyme Inhibitors;Isaac B. Bersuker等;《Journal of Chemical Information and Modeling》;20000907;第40卷(第6期);第1374页化合物T21 * |
| NIPALSTREE: A New Hierarchical Clustering Approach for Large Compound libraries and Its Application to Virtual Screening;Alexander Bocker等;《Jounarl of Chemical Information and Modeling》;20060324;第46卷(第6期);第2225页右栏化合物5C * |
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