Golden serial low-luster sheet layer pigment and preparation method thereofTechnical field
The invention belongs to fine chemistry industry Material Field, be specifically related to a kind of golden serial low-luster sheet layer pigment and preparation method thereof.
Background technology
At present, the pigment that market is sold is mostly pearly pigment, pearly pigment can reproduce the graceful gloss and color that nature pearl, shell, metal, swimming fish and butterfly have, it relies on the refraction to light, reflection, projection to create form and aspect and gloss, can give plastics, leather etc. with deep gradation sense and special reflecting feel.But what adopt due to pearly pigment is all that Large stone (its particle diameter is all more than 10 μm) mica particles is made as pigment substrate, and the surface coating layer of this substrate is mostly the Nano titanium dioxide of the distribution in island, therefore its skinfeel is poor, thus limits its application in each field.
Pigment skinfeel is being carried out in the research process of modification, although the very large reason of pearly pigment skinfeel difference is from the size of its pigment substrate particle diameter, in the industry, is but rarely having the pigment substrate giving up Large stone to select small particle size, especially median size D50the research that the little superfine mica particles to 1 μm ~ 6 μm carries out being correlated with as pigment substrate.This is because first, when pigment particle size is less than 1 μm ~ 6 μm, prepared pearly pigment glossiness is very low, its glossiness in dumb light scope, so pearly pigment produce and researchist think do not have research necessity; Secondly, in the process preparing pigment using small particle size mica particles as pigment substrate, there is following technical barrier: 1. the preparation of small particle size mica is complicated, and cost is higher, thus is considered to do not have researching value; 2. when the particle diameter of mica powder substrate little to 1 μm ~ 6 μm time, it is when follow-up drying and calcining, be very easy to reunite and formed have compared with high bond strength and the misconduct particle of reuniting, thus lose required laminar pigment performance; 3., when mica particles substrate coated with metal oxide particle, metal oxide particle size is sprawled form with it in surface of pigments and is difficult to control.
Summary of the invention
One of technical problem to be solved by this invention be to provide a kind of using superfine mica particles as pigment substrate, there is unique matte effect and have the gold series low gloss sheet layer pigment of fine and smooth soft and smooth and pro-skin.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: with median size D50be the mica powder of 1 μm ~ 6 μm as substrate, and at one or more layers metal oxide of Surface coating of described substrate.
In technique scheme, technical scheme can also be more specifically: described metal oxide is TiO2and Fe2o3.
Further, the clad ratio of coating of metal oxides is 60% ~ 95%.
Two of technical problem to be solved by this invention is to provide the preparation method of the gold series low gloss sheet layer pigment that a kind of preparation technology is simple, relevance grade is high.
In order to solve the problem, the technical solution adopted in the present invention is:
Comprise the following steps:
A. by median size D50be that the mica powder of 1 μm ~ 6 μm and crystal grain conditioning agent drop in deionized water, make suspension; Wherein, the consumption of described crystal grain conditioning agent is 0.01% ~ 2% of mica powder quality;
B. under agitation successively by SnCl45H2o solution, TiCl4solution and FeCl3solution measures joins in the obtained suspension of steps A;
C. when the color of described step B suspension reaches required form and aspect, regulate its pH value to 1.5 ~ 3.5, under constant temperature agitation condition, then add the pigment antiadhesives of mica powder quality 0.01% ~ 5%, and it is constant to control the maintenance of its pH value;
D., after step C terminates, continue constant temperature at 65 DEG C ~ 85 DEG C and stir 15 minutes ~ 30 minutes, then by obtained suspension filtered, drying, calcining.
In technique scheme, technical scheme is more specifically:
Further, the electric conductivity of the deionized water used in described step A is less than 20 μ S/cm.
Further, wherein SnCl described in a kind of step B45H2o solution, TiCl4solution and FeCl3the concrete Adding Way of solution is as follows:
A. suspension is warming up to 65 DEG C ~ 80 DEG C, and the pH value of described suspension is regulated 1.5, under constant temperature stirs, then add the SnCl of described mica powder quality 0.5%45H2o solution, and keep pH value constant in the process; As described SnCl45H2after the interpolation of O solution terminates, continue constant temperature and stir 15 minutes ~ 30 minutes;
B. the suspension after step A process is warming up to 75 DEG C ~ 80 DEG C, and the pH value of described suspension is regulated 1.8 ~ 2.0, then under constant temperature stirs, add TiCl4solution until the color of described suspension becomes weak golden, and keeps pH value constant in the process; As described TiCl4after solution interpolation terminates, continue constant temperature and stir 15 minutes ~ 30 minutes;
C. the suspension after D step process is warming up to 75 DEG C ~ 80 DEG C, and the pH value of described suspension is regulated 2.5 ~ 3.3, then under constant temperature stirs, add FeCl3solution until the color of described suspension becomes required form and aspect, and keeps pH value constant in the process.
Further, SnCl described in another kind of step B45H2o solution, TiCl4solution and FeCl3the concrete Adding Way of solution is as follows:
A. suspension is warming up to 65 DEG C, and the pH value of described suspension is regulated 1.5, under constant temperature stirs, then add the SnCl of described mica powder quality 0.5%45H2o solution, and keep pH value constant in the process; As described SnCl45H2after the interpolation of O solution terminates, continue constant temperature and stir 15 minutes ~ 30 minutes;
B. the suspension after step A process is warming up to 75 DEG C ~ 80 DEG C, and the pH value of described suspension is regulated 2.2 ~ 2.5, then add by TiCl under constant temperature stirs4solution and FeCl3solution is mixed to get solution until the color of described suspension becomes required form and aspect, and keep pH value constant in the process.
Owing to adopting technique scheme, the beneficial effect that the present invention obtains is:
1. the present invention is owing to adopting median size D50be that the superfine mica particles of 1 μm ~ 6 μm is as substrate, and at one or more layers metal oxide of Surface coating of described substrate, its clad ratio is made to reach 60% ~ 95%, thus obtain having fine and smooth soft and smooth, pro-skin effect is fairly obvious, and the pigment of the high sheet structure of opacifying power, can be widely used in makeup, leather, plastics, ink and coating.
2. preparation technology of the present invention is simple, relevance grade is high, can need the golden series product preparing blue or green gold, the positive various form and aspect such as gold and red gold according to the difference of client.
3. deionized water electric conductivity is defined as and is less than 20 μ S/cm by the present invention, can effectively reduce the impact on metal oxide hydrolytic process.
4. in the present invention, tin-salt solution plays the effect crystal formation of titanium dioxide being changed into rutile-type by anatase titanium dioxide.
5. in the present invention, crystal grain conditioning agent is general has the compound referring to suppress or promote metal oxide hydrolytic action; The present invention is by adding crystal grain conditioning agent and controlling its consumption, control metal oxide and be deposited on size on base material, make the metal oxide particle at one or more layers nanoscale of fine grain size mica substrate Surface coating, even compact, and clad ratio is high.
6. the present invention is by adding pigment antiadhesives and controlling its consumption, effective prevention pigment particles adheres to each other, make coated after granules of pigments not easily tie grain, and form uniform sheet dispersed texture, thus there is larger specific surface area, there is certain transparency, and there is unglazed or matte effect simultaneously, well can be applied at cosmetic industry.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the pigment top layer coating particle characterization that the embodiment of the present invention 1 obtains.
Fig. 2 is the SEM figure of the pigment top layer coating particle characterization that the embodiment of the present invention 2 obtains.
Fig. 3 is the SEM figure of the pigment top layer coating particle characterization that the embodiment of the present invention 3 obtains.
Fig. 4 is the SEM figure of the pigment top layer coating particle characterization that the embodiment of the present invention 4 obtains.
Fig. 5 is the SEM figure of the pigment top layer coating particle characterization that the embodiment of the present invention 5 obtains.
Fig. 6 is the SEM figure of the pigment top layer coating particle characterization that the embodiment of the present invention 6 obtains.
Embodiment
In order to better the present invention is described, below in conjunction with specific embodiment, the invention will be further described, and protection scope of the present invention is not only confined to following examples.
Embodiment 1
The preparation method of capital color system low-luster sheet layer pigment comprises the following steps:
A. take the natural mica that 25g median size is 3.1 μm, putting into volume is in the reactor of 2L, adds 900ml deionized water and polyoxyethylene glycol 0.1g, stirs and makes it dispersed formation suspension;
B. the suspension after step A process is warming up to 65 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 1.5, then under constant temperature stirs, slowly drip 3%(wt) SnCl45H2o50ml, and drip 20% sodium hydroxide in the process to keep pH value constant; As described SnCl45H2after the interpolation of O solution terminates, continue constant temperature and stir 20 minutes;
C. the suspension after step B process is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 1.8, then under constant temperature stirs, add 1.6mol/LTiCl4solution until the color of described suspension becomes weak golden, and drips 20% sodium hydroxide in the process to keep pH value constant; As described TiCl4after solution interpolation terminates, continue constant temperature and stir 20 minutes;
D. the suspension after step C process is warming up to 78 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 3.1, then under constant temperature stirs, add 0.8mol/LFeCl3solution until the color of described suspension becomes reddish gold, and drips 20% sodium hydroxide in the process to keep pH value constant;
E. when described D step suspension dilute hydrochloric acid regulates its pH value to 5.5, then under constant temperature agitation condition, add 0.25g sodium laurylsulfonate, and it is constant to control the maintenance of its pH value;
F. after step e terminates, constant temperature stirs 30 minutes, and then by suspension filtered, 105 DEG C of dryings, calcine 5 minutes for 780 DEG C, sampling washing, 105 DEG C of dryings.
The present embodiment obtains positive golden low-luster sheet layer pigment.
Embodiment 2
The preparation method of capital color system low-luster sheet layer pigment comprises the following steps:
A. take the natural mica that 25g median size is 1.0 μm, putting into volume is in the reactor of 2L, adds 900ml deionized water and polyoxyethylene glycol 0.0025g, stirs and makes it dispersed formation suspension;
B. the suspension after step A process is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 1.5, then under constant temperature stirs, slowly drip 3%(wt) SnCl45H2o50ml, and drip 20% sodium hydroxide in the process to keep pH value constant; As described SnCl45H2after the interpolation of O solution terminates, continue constant temperature and stir 30 minutes;
C. the suspension after step B process is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 1.9, then under constant temperature stirs, add 1.6mol/LTiCl4solution until the color of described suspension becomes weak golden, and drips 20% sodium hydroxide in the process to keep pH value constant; As described TiCl4after solution interpolation terminates, continue constant temperature and stir 15 minutes;
D. the suspension after step C process is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 2.5, then under constant temperature stirs, add 0.8mol/LFeCl3solution until the color of described suspension becomes reddish gold, and drips 20% sodium hydroxide in the process to keep pH value constant;
E. when described D step suspension dilute hydrochloric acid regulates its pH value to 3, then under constant temperature agitation condition, add 0.0025g sodium laurylsulfonate, and it is constant to control the maintenance of its pH value;
F. after step e terminates, constant temperature stirs 30 minutes, and then by suspension filtered, 105 DEG C of dryings, calcine 5 minutes for 780 DEG C, sampling washing, 105 DEG C of dryings.
The present embodiment obtains positive golden low-luster sheet layer pigment.
Embodiment 3
The preparation method of capital color system low-luster sheet layer pigment comprises the following steps:
A. take the natural mica that 25g median size is 6 μm, putting into volume is in the reactor of 2L, adds 900ml deionized water and urea 0.5g, stirs and makes it dispersed formation suspension;
B. the suspension after step A process is warming up to 80 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 1.5, then under constant temperature stirs, slowly drip 3%(wt) SnCl45H2o50ml, and drip 20% sodium hydroxide in the process to keep pH value constant; As described SnCl45H2after the interpolation of O solution terminates, continue constant temperature and stir 30 minutes;
C. the suspension after step B process is warming up to 80 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 2.0, then under constant temperature stirs, add 1.6mol/LTiCl4solution until the color of described suspension becomes weak golden, and drips 20% sodium hydroxide in the process to keep pH value constant; As described TiCl4after solution interpolation terminates, continue constant temperature and stir 30 minutes;
D. the suspension after step C process is warming up to 80 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 3.3, then under constant temperature stirs, add 0.8mol/LFeCl3solution until the color of described suspension becomes reddish gold, and drips 20% sodium hydroxide in the process to keep pH value constant;
E. when described D step suspension dilute hydrochloric acid regulates its pH value to 3.8, then under constant temperature agitation condition, add 0.25g chitosan, and it is constant to control the maintenance of its pH value;
F. after step e terminates, constant temperature stirs 20 minutes, and then by suspension filtered, 105 DEG C of dryings, calcine 5 minutes for 780 DEG C, sampling washing, 105 DEG C of dryings.
The present embodiment obtains positive golden low-luster sheet layer pigment.
Embodiment 4
The preparation method of capital color system low-luster sheet layer pigment comprises the following steps:
A. take the natural mica that 25g median size is 3.2 μm, putting into volume is in the reactor of 2L, adds 900ml deionized water and urea 0.3g, stirs and makes it dispersed formation suspension;
B. the suspension after step A process is warming up to 65 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 1.5, then under constant temperature stirs, slowly drip 3%(wt) SnCl45H2o50ml, and drip 20% sodium hydroxide in the process to keep pH value constant; As described SnCl45H2after the interpolation of O solution terminates, continue constant temperature and stir 20 minutes;
C. the suspension after step B process is warming up to 75 DEG C, and the pH value of described suspension is regulated 2.5, then under constant temperature stirs, add 2mol/LTiCl4and 0.8mol/LFeCl3mixing solutions until the color of described suspension becomes scarlet, and in the process keep pH value constant;
D. when described step C suspension dilute hydrochloric acid regulates its pH value to 7, then under constant temperature agitation condition, add 0.25g chitosan, and it is constant to control the maintenance of its pH value;
E. after step D terminates, constant temperature stirs 15 minutes, and then by suspension filtered, 105 DEG C of dryings, calcine 5 minutes for 780 DEG C, sampling washing, 105 DEG C of dryings.
The present embodiment obtains the golden low-luster sheet layer pigment of the red phase of band.
Embodiment 5
The preparation method of capital color system low-luster sheet layer pigment comprises the following steps:
A. take the natural mica that 25g median size is 6 μm, putting into volume is in the reactor of 2L, adds 900ml deionized water and polyoxyethylene glycol 0.0025g, stirs and makes it dispersed formation suspension;
B. the suspension after step A process is warming up to 80 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 1.5, then under constant temperature stirs, slowly drip 3%(wt) SnCl45H2o50ml, and drip 20% sodium hydroxide in the process to keep pH value constant; As described SnCl45H2after the interpolation of O solution terminates, continue constant temperature and stir 30 minutes;
C. the suspension after step B process is warming up to 78 DEG C, and the pH value of described suspension is regulated 2.0, then under constant temperature stirs, add 2mol/LTiCl4and 0.8mol/LFeCl3mixing solutions until the color of described suspension becomes scarlet, and in the process keep pH value constant;
D. when described step C suspension dilute hydrochloric acid regulates its pH value to 6, then under constant temperature agitation condition, add 1.25g sodium laurylsulfonate, and it is constant to control the maintenance of its pH value;
E. after step D terminates, constant temperature stirs 15 minutes, and then by suspension filtered, 105 DEG C of dryings, calcine 5 minutes for 780 DEG C, sampling washing, 105 DEG C of dryings.
The present embodiment obtains the golden low-luster sheet layer pigment of the red phase of band.
Embodiment 6
The preparation method of capital color system low-luster sheet layer pigment comprises the following steps:
A. take the natural mica that 25g median size is 4 μm, putting into volume is in the reactor of 2L, adds 900ml deionized water and polyoxyethylene glycol 0.5g, stirs and makes it dispersed formation suspension;
B. the suspension after step A process is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is adjusted to 1.5, then under constant temperature stirs, slowly drip 3%(wt) SnCl45H2o50ml, and drip 20% sodium hydroxide in the process to keep pH value constant; As described SnCl45H2after the interpolation of O solution terminates, continue constant temperature and stir 15 minutes;
C. the suspension after step B process is warming up to 80 DEG C, and the pH value of described suspension is regulated 3.0, then under constant temperature stirs, add 2mol/LTiCl4and 0.8mol/LFeCl3mixing solutions until the color of described suspension becomes reddish gold, and in the process keep pH value constant;
D. when described step C suspension dilute hydrochloric acid regulates its pH value to 3.75, then under constant temperature agitation condition, add 0.25g chitosan, and it is constant to control the maintenance of its pH value;
E. after step D terminates, constant temperature stirs 15 minutes, and then by suspension filtered, 105 DEG C of dryings, calcine 5 minutes for 780 DEG C, sampling washing, 105 DEG C of dryings.
The present embodiment obtains positive golden low-luster sheet layer pigment.
Detected result
One, the detection of glossiness:
(1) pigment model preparation: by pigment and resin in 1:10(mass ratio) ratio mix well, and with 25 μm of thick film applicator blade coatings on blackboard colour table, at 105 DEG C, dry 10min.
(2) glossiness detecting instrument: BGD515 type three angle glossometer (20 ° 60 ° 85 °), Guangzhou style reaches experiment
Room instrument articles for use company limited.
(3) detection of glossiness: under this instrument being adjusted to 60 ° of angles, the gloss value of experiments of measuring sample on white base plate.
(4) result: the detected result of the pigment product that embodiment 1 ~ 6 is obtained is as table 1:
Table 1
note: glossiness < 20, then belong to dumb light series (the less glossiness of particle diameter is lower)
As can be seen from the above Table 1, this golden serial low-luster sheet layer pigment matte effect is remarkable.
Two, pigment top layer characterizes coating particle characterization
Can find out from Fig. 1 to Fig. 6, granules of pigments does not bond agglomerating, is dispersion, in the form of sheets structure between them.