A kind of modified microorganism/vegetable colour composition of particulate oxidation graphene and its
Preparation method
Technical field
The invention belongs to daily cosmetics technical fields, and in particular to a kind of micro- life that particulate oxidation graphene is modified
Object/vegetable colour composition and preparation method thereof.
Background technique
Pigment is widely used in cosmetic field, and pigment can be divided into synthetic dyestuff and natural pigment, wherein secondary colour
Element have many advantages, such as wide in variety, chromatography is complete, stability is good, it is bright in colour, can be mass-produced, but synthetic dyestuff and
The by-product generated in their production processes is bigger to the harm of human health and environment, and natural pigment has safe nothing
Poison, non-carcinogenesis and it is biodegradable the advantages that, therefore, natural pigment is in cosmetic field using more and more.
There are animals and plants, mineral, insect, microorganism etc. in the source of natural pigment, and wherein microbe species are various, and source is wide
General, microorganism is through cometabolism can deep layer be red, orange, yellow, green, cyan, blue, purple, black and brown etc. are a variety of
Water-soluble or water-insoluble microorganisms pigments, it is at low cost, with short production cycle compared with other source natural pigments and not by ring
The limitation in condition domain is suitable for industrializing a wide range of production, and therefore, microorganisms pigments are as natural colorant in cosmetic field
Have broad application prospects.
The disclosed colouring compositions comprising Myceliophthora laccase of Chinese patent CN 1084357C, the permanent dyeing
Composition include Myceliophthora laccase, one or more kinds of dyestuff former (p-phenylenediamine, to toluylene diamine, chlorine p-phenylenediamine,
Para-aminophenol, o-aminophenol, 3,4- diaminotoluene, 2- methyl-1,4- diaminobenzene, 4- methyl-o-phenylenediamine, 2- first
The chloro- 1,4- diaminobenzene of oxygroup-p-phenylenediamine, 2-, 4-ADPA, 1- amino -4- 'beta '-methoxy ethyl amino phenyl, 1- ammonia
- 4- pairs, base-(beta-hydroxyethyl)-aminobenzene, 1,3- diaminobenzene, 2- methyl-1,3- diaminobenzene, 2,4 di amino toluene, 2,
6- diamino-pyridine, 1- hydroxyl -2- aminobenzene, 1- hydroxyl -3- aminobenzene, 1- methyl -2- hydroxyl -4- aminobenzene, 1- methyl -2-
Hydroxyl -4- beta-hydroxyethyl aminobenzene, 1- hydroxyl -4- aminobenzene, 1- hydroxy-4-methyl aminobenzene, 1- methoxyl group -2,4- diamino
Benzene, 1- ethyoxyl -2,3- diaminobenzene, 1- beta-hydroxy ethyoxyl -2,4- diaminobenzene, azophenlyene, p-aminobenzoic acid class, isatin
Derivative), dye molecule modifying agent (m-phenylene diamine (MPD), 2,4- diamino anisole, 1- hydroxyl naphthalene (alpha-Naphthol), 1,4- dihydroxy
Benzene (quinhydrones), 1,5- dihydroxy naphthlene, 1,2- dihydroxy benzenes (catechol), 1,3- dihydroxy benzenes (resorcinol), 1,3- dihydroxy
Base -2- methylbenzene, 1,3- dihydroxy -4- chlorobenzene (4- chloro resorcinol), Pyrogallic acid, 1,2,4- dihydroxy benzenes, 1,
2,4- trihydroxy -5- methylbenzenes, 1,2,4- trihydroxytoluenes), which can be used for hair, fur, animal skin and wool isogonism egg
White fiber dyeing.But microbial dye, when being applied in cosmetics, comprehensive dyeing effect and biological safety are always to make up
The major issue of product dyeing.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of modified microorganism/vegetable colours of particulate oxidation graphene
Composition and preparation method thereof, the present invention make to combine to obtain with laccase and graphene oxide by the vegetable colour of liquid state fermentation,
Fermented by mixed bacterium of the middle vegetable colour through its rhizosphere soil culture is more thoroughly efficient, and molecular weight is smaller, is conducive to aoxidizing
Graininess colouring compositions are formed under the reunion and cladding of graphene, improve the stability, dyeing effect and biology peace of dyestuff
Quan Xing.
In order to solve the above technical problems, the technical scheme is that
A kind of microorganism/vegetable colour composition preparation method that particulate oxidation graphene is modified, including following step
It is rapid:
(1) dye-type plant is connected rhizosphere soil to dig out, rhizosphere soil is removed from dye-type plant surface, obtains dyestuff
Type plant and rhizosphere soil;
(2) by step (1) prepare dye-type plant rinse well after, after chopping up, supersonic wave wall breaking processing, addition go from
Sub- water dilution, stirs evenly, and filtering removal granule foreign, sterilizing obtains dye-type plant slurry;
(3) rhizosphere soil by step (1) preparation is added in culture medium, screens using nine wheels, obtains mix bacterium agent;
(4) the dye-type plant slurry of step (2) preparation will be added after the mix bacterium agent enrichment culture of step (3) preparation
In, liquid state fermentation, centrifugation obtains plant type fermentation dyestuff;
(5) graphene oxide water solution containing laccase, mixing will be added in the plant type fermentation dyestuff of step (4) preparation
After uniformly, the modified microorganism/vegetable colour composition of particulate oxidation graphene is obtained.
As a preferred embodiment of the above technical solution, in the step (1), rhizosphere soil is with dye-type plant center 8-10cm
The soil for removing skim-coat.
As a preferred embodiment of the above technical solution, in the step (1), dye-type plant is green system, yellow class, red
The plant of system, brown system or black system.
As a preferred embodiment of the above technical solution, in the step (2), the technique of supersonic wave wall breaking processing are as follows: first in 25-30
It at DEG C, to handle 10-15min under 600-800W power, then heats at 30-45 DEG C, to handle 5- under 800-1000W power
10min, finally at 50-60 DEG C, to handle 5-15min under 1000-1500W power.
As a preferred embodiment of the above technical solution, in the step (2), the aperture of filtering is 0.6-0.8 μm.
It as a preferred embodiment of the above technical solution, include yeast and lactic acid bacteria in mix bacterium agent in the step (3).
As a preferred embodiment of the above technical solution, in the step (4), the mass ratio of mix bacterium agent and dye-type plant slurry
For 1-5:100.
As a preferred embodiment of the above technical solution, in the step (4), the technique of liquid state fermentation are as follows: first in the case where pH is 3-4,
With the 1-3h that ferments at 20-25 DEG C, then in the case where pH is 4-6, with the 2-6h that ferments at 25-30 DEG C, finally in the case where pH is 6-7, with 30-
Ferment 6-8h at 35 DEG C.
As a preferred embodiment of the above technical solution, in the step (4), the modified microorganism/plant of particulate oxidation graphene
The content of graphene oxide is 5-8mg/mL in object dye composite, and the content of laccase is 3-7wt%.
The modified microorganism of any one particulate oxidation graphene described above/plant dye is also claimed in the present invention
Modified microorganism/vegetable colour the composition of the particulate oxidation graphene of the preparation of feed composition.
Modified microorganism/vegetable colour the composition of particulate oxidation graphene prepared by the present invention can be used as cosmetics dye
Toner use, particularly suitable as quickly having hair dyed, highlighting and mascara use.
Compared with prior art, the invention has the following advantages:
(1) the modified microorganism/vegetable colour composition of particulate oxidation graphene prepared by the present invention includes plant dye
Material, microbial dye and graphene oxide, wherein vegetable colour is the mix bacterium agent using plant rhizosphere soil culture to dyestuff
Type plant liquid state fermentation forms, and fermentation is more thoroughly efficient, keeps the molecular weight of the vegetable colour of preparation smaller, is conducive to improve dye
The permeability and dispersing uniformity of material improve the dye-uptake of vegetable colour and the uniformity of upper dye, the microorganism furthermore contained
Dyestuff belongs to different dyeing mechanism from vegetable colour, can be dyed simultaneously, and the efficiency and upper dye of dyeing are further increased
Rate, and the graphene oxide being added has big specific surface area, vegetable colour and microbial dye can be adsorbed onto surface,
Again by the agglomeration of nano material itself, especially multilayer graphene oxide be easier vegetable colour and microbial dye into
Row is overmolding to graininess, reduces the contact rate of vegetable colour and microbial dye and skin, improves biological safety afterwards,
Also improve dye composite wash durability and sun-proof performance, and formed graininess colouring compositions relative to tradition
Dyestuff still there is biggish specific surface area, the surface layer that more conducively graininess dye composite infiltrates through hair enters inside, into
One step accelerates the efficiency of dyeing, improves the service efficiency of vegetable colour and microbial dye
(2) therefore, the modified microorganism/vegetable colour of particulate oxidation graphene prepared by the present invention
Composition stability is good, and dyeing rate is fast, and dyeing uniformity is good, and color is good, and water-fast light resistance is good, and biological safety is good, comprehensive
Conjunction is had excellent performance, can be used as cosmetic coloration agent use, particularly suitable as quickly having hair dyed, highlighting and mascara use.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1:
(1) green based dye type plant is even dug out with the rhizosphere soil for removing skim-coat of dye-type plant center 8cm, it will
Rhizosphere soil is removed from dye-type plant surface, obtains dye-type plant and rhizosphere soil.
(2) it after rinsing dye-type plant well, after chopping up, is placed in supersonic wave wall breaking device, first at 25 DEG C, with 600W
10min is handled under power, is then heated at 30 DEG C, to handle 5min under 800W power, finally at 50 DEG C, with 1000W function
5min is handled under rate, and deionized water dilution is added, stirs evenly, the filter membrane filtering removal granule foreign that via hole diameter is 0.6 μm,
Sterilizing, obtains dye-type plant slurry.
(3) rhizosphere soil is added in culture medium, is screened using nine wheels, obtaining includes yeast and lactic acid bacteria mix bacterium agent.
It (4) is 1:100 according to the mass ratio of mix bacterium agent and dye-type plant slurry by after mix bacterium agent enrichment culture,
It is added in dye-type plant slurry, first in the case where pH is 3, with the 1h that ferments at 20 DEG C, then in the case where pH is 4, with the 2h that ferments at 25 DEG C,
Finally in the case where pH is 6, with the 6h that ferments at 30 DEG C, centrifugation obtains plant type fermentation dyestuff.
(5) plant type is fermented and the graphene oxide water solution containing laccase is added in dyestuff, after mixing, obtained
Modified microorganism/vegetable colour the composition of granular graphene oxide, wherein the modified microorganism of particulate oxidation graphene/
The content of graphene oxide is 5mg/mL in vegetable colour composition, and the content of laccase is 3wt%.
Embodiment 2:
(1) yellow class dye-type plant is even dug out with the rhizosphere soil for removing skim-coat of dye-type plant center 10cm,
Rhizosphere soil is removed from dye-type plant surface, obtains dye-type plant and rhizosphere soil.
(2) it after rinsing dye-type plant well, after chopping up, is placed in supersonic wave wall breaking device, first at 30 DEG C, with 800W
15min is handled under power, is then heated at 45 DEG C, to handle 10min under 1000W power, finally at 60 DEG C, with 1500W
15min is handled under power, deionized water dilution is added, stirs evenly, and the filter membrane filtering removal particle that via hole diameter is 0.8 μm is miscellaneous
Matter, sterilizing, obtains dye-type plant slurry.
(3) rhizosphere soil is added in culture medium, is screened using nine wheels, obtaining includes yeast and lactic acid bacteria mix bacterium agent.
It (4) is 5:100 according to the mass ratio of mix bacterium agent and dye-type plant slurry by after mix bacterium agent enrichment culture,
It is added in dye-type plant slurry, first in the case where pH is 4, with the 3h that ferments at 25 DEG C, then in the case where pH is 6, with the 6h that ferments at 30 DEG C,
Finally in the case where pH is 7, with the 8h that ferments at 35 DEG C, centrifugation obtains plant type fermentation dyestuff.
(5) plant type is fermented and the graphene oxide water solution containing laccase is added in dyestuff, after mixing, obtained
Modified microorganism/vegetable colour the composition of granular graphene oxide, wherein the modified microorganism of particulate oxidation graphene/
The content of graphene oxide is 8mg/mL in vegetable colour composition, and the content of laccase is 7wt%.
Embodiment 3:
(1) red colour system dye-type plant is even dug out with the rhizosphere soil for removing skim-coat of dye-type plant center 9cm, it will
Rhizosphere soil is removed from dye-type plant surface, obtains dye-type plant and rhizosphere soil.
(2) it after rinsing dye-type plant well, after chopping up, is placed in supersonic wave wall breaking device, first at 28 DEG C, with 700W
14min is handled under power, is then heated at 35 DEG C, to handle 8min under 900W power, finally at 55 DEG C, with 1300W function
10min is handled under rate, deionized water dilution is added, stirs evenly, and the filter membrane filtering removal particle that via hole diameter is 0.7 μm is miscellaneous
Matter, sterilizing, obtains dye-type plant slurry.
(3) rhizosphere soil is added in culture medium, is screened using nine wheels, obtaining includes yeast and lactic acid bacteria mix bacterium agent.
It (4) is 2:100 according to the mass ratio of mix bacterium agent and dye-type plant slurry by after mix bacterium agent enrichment culture,
It is added in dye-type plant slurry, first in the case where pH is 3.4, with the 2h that ferments at 23 DEG C, then in the case where pH is 5.5, is issued with 28 DEG C
Ferment 4h, finally in the case where pH is 6.5, with the 7h that ferments at 34 DEG C, centrifugation obtains plant type fermentation dyestuff.
(5) plant type is fermented and the graphene oxide water solution containing laccase is added in dyestuff, after mixing, obtained
Modified microorganism/vegetable colour the composition of granular graphene oxide, wherein the modified microorganism of particulate oxidation graphene/
The content of graphene oxide is 6mg/mL in vegetable colour composition, and the content of laccase is 5wt%.
Embodiment 4:
(1) brown based dye type plant is even dug out with the rhizosphere soil for removing skim-coat of dye-type plant center 9.5cm,
Rhizosphere soil is removed from dye-type plant surface, obtains dye-type plant and rhizosphere soil.
(2) it after rinsing dye-type plant well, after chopping up, is placed in supersonic wave wall breaking device, first at 28 DEG C, with 750W
14min is handled under power, is then heated at 40 DEG C, to handle 8min under 950W power, finally at 54 DEG C, with 1350W function
10min is handled under rate, deionized water dilution is added, stirs evenly, and the filter membrane filtering removal particle that via hole diameter is 0.65 μm is miscellaneous
Matter, sterilizing, obtains dye-type plant slurry.
(3) rhizosphere soil is added in culture medium, is screened using nine wheels, obtaining includes yeast and lactic acid bacteria mix bacterium agent.
It (4) is 3:100 according to the mass ratio of mix bacterium agent and dye-type plant slurry by after mix bacterium agent enrichment culture,
It is added in dye-type plant slurry, first in the case where pH is 3.7, with the 2h that ferments at 21 DEG C, then in the case where pH is 5.5, is issued with 28 DEG C
Ferment 5h, finally in the case where pH is 6.3, with the 7.5h that ferments at 33 DEG C, centrifugation obtains plant type fermentation dyestuff.
(5) plant type is fermented and the graphene oxide water solution containing laccase is added in dyestuff, after mixing, obtained
Modified microorganism/vegetable colour the composition of granular graphene oxide, wherein the modified microorganism of particulate oxidation graphene/
The content of graphene oxide is 6.5mg/mL in vegetable colour composition, and the content of laccase is 5wt%.
Embodiment 5:
(1) black based dye type plant is even dug out with the rhizosphere soil for removing skim-coat of dye-type plant center 8cm, it will
Rhizosphere soil is removed from dye-type plant surface, obtains dye-type plant and rhizosphere soil.
(2) it after rinsing dye-type plant well, after chopping up, is placed in supersonic wave wall breaking device, first at 30 DEG C, with 600W
15min is handled under power, is then heated at 30 DEG C, to handle 5min under 1000W power, finally at 60 DEG C, with 1000W function
15min is handled under rate, deionized water dilution is added, stirs evenly, and the filter membrane filtering removal particle that via hole diameter is 0.6 μm is miscellaneous
Matter, sterilizing, obtains dye-type plant slurry.
(3) rhizosphere soil is added in culture medium, is screened using nine wheels, obtaining includes yeast and lactic acid bacteria mix bacterium agent.
It (4) is 5:100 according to the mass ratio of mix bacterium agent and dye-type plant slurry by after mix bacterium agent enrichment culture,
It is added in dye-type plant slurry, first in the case where pH is 3, with the 1h that ferments at 25 DEG C, then in the case where pH is 6, with the 6h that ferments at 25 DEG C,
Finally in the case where pH is 6, with the 6h that ferments at 35 DEG C, centrifugation obtains plant type fermentation dyestuff.
(5) plant type is fermented and the graphene oxide water solution containing laccase is added in dyestuff, after mixing, obtained
Modified microorganism/vegetable colour the composition of granular graphene oxide, wherein the modified microorganism of particulate oxidation graphene/
The content of graphene oxide is 8mg/mL in vegetable colour composition, and the content of laccase is 3wt%.
Embodiment 6:
(1) black based dye type plant is even dug out with the rhizosphere soil for removing skim-coat of dye-type plant center 10cm,
Rhizosphere soil is removed from dye-type plant surface, obtains dye-type plant and rhizosphere soil.
(2) it after rinsing dye-type plant well, after chopping up, is placed in supersonic wave wall breaking device, first at 25 DEG C, with 800W
10min is handled under power, is then heated at 45 DEG C, to handle 10min under 800W power, finally at 50 DEG C, with 1500W function
5min is handled under rate, and deionized water dilution is added, stirs evenly, the filter membrane filtering removal granule foreign that via hole diameter is 0.8 μm,
Sterilizing, obtains dye-type plant slurry.
(3) rhizosphere soil is added in culture medium, is screened using nine wheels, obtaining includes yeast and lactic acid bacteria mix bacterium agent.
It (4) is 1:100 according to the mass ratio of mix bacterium agent and dye-type plant slurry by after mix bacterium agent enrichment culture,
It is added in dye-type plant slurry, first in the case where pH is 4, with the 3h that ferments at 20 DEG C, then in the case where pH is 4, with the 2h that ferments at 30 DEG C,
Finally in the case where pH is 7, with the 8h that ferments at 30 DEG C, centrifugation obtains plant type fermentation dyestuff.
(5) plant type is fermented and the graphene oxide water solution containing laccase is added in dyestuff, after mixing, obtained
Modified microorganism/vegetable colour the composition of granular graphene oxide, wherein the modified microorganism of particulate oxidation graphene/
The content of graphene oxide is 5mg/mL in vegetable colour composition, and the content of laccase is 7wt%.
Through detecting, microorganism/vegetable colour composition that the particulate oxidation graphene of embodiment 1-6 preparation is modified is flat
The result of equal particle size and dyeing effect is as follows:
|
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Embodiment 4 |
Embodiment 5 |
Embodiment 6 |
Average particle diameter size (μm) |
158 |
275 |
184 |
238 |
250 |
183 |
The time (min) that dye-uptake is 80% |
23 |
46 |
38 |
32 |
41 |
29 |
Maximum dye-uptake (%) |
92 |
98 |
94 |
95 |
93 |
94 |
The color retention (%) that washing is 50 times |
94 |
99 |
95 |
96 |
95 |
96 |
Color retention (%) after sunshine 100h |
99 |
98 |
99 |
97 |
98 |
99 |
As seen from the above table, the modified microorganism/vegetable colour composition of particulate oxidation graphene prepared by the present invention
Stability is good, and dyeing rate is fast, and dyeing uniformity is good, and color is good, and water-fast light resistance is good.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.