CN103788720B - Method for preparing metal coated pearlescent pigment - Google Patents
Method for preparing metal coated pearlescent pigment Download PDFInfo
- Publication number
- CN103788720B CN103788720B CN201410052460.9A CN201410052460A CN103788720B CN 103788720 B CN103788720 B CN 103788720B CN 201410052460 A CN201410052460 A CN 201410052460A CN 103788720 B CN103788720 B CN 103788720B
- Authority
- CN
- China
- Prior art keywords
- pearly pigment
- receive
- preparation
- rice
- rod
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Cosmetics (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a method for preparing a metal coated pearlescent pigment. The pearlescent pigment is characterized by comprising a flaky substrate and a plurality of titanium dioxide nanorods which are arranged at intervals and are formed on the flaky substrate, so that a nano-structured surface with roughness can be formed by the titanium dioxide nanorods of the pearlescent pigment, and then, a plurality of metal particles are deposited on each titanium dioxide nanorod and the flaky substrate respectively.
Description
Technical field
The invention belongs to pearly pigment field, relate to a kind of powder pigments, particularly relate to pearly pigment of a kind of metallic cover and preparation method thereof.
Background technology
Pearly pigment has the pigment giving goods pearlescent, it is for core with transparent or translucent thin slice, adopt the film that special chemical technology is formed at one or more layers titanium dioxide of its Surface coating and other metal oxide, when irradiate light is to pearly pigment interface, reflected light and refracted light can be produced, reflect again after some light transmission, between them, mutually interfere generation one to have relief pearly-lustre color.Do base material mainly with mica sheet greatly at present, the coating of titanium dioxide of the coated height refraction in outside, reflected by titanium dioxide layer segment when time on the pigment that white light is irradiated to this type, remaining light then arrives at mica surface through (refraction) titanium dioxide layer, then some light is reflected again, is parallel to first reflection ray and leaves surface of pigments.The light wave of second light has partial offset with first light relatively, different according to the length of institute's route via, bias size difference.If crest and crest superposition, trough and trough superposition, will strengthen light wave.By applying the titanium dioxide of different thickness on mica, can obtain from silvery white, through yellow, red, blue, until green (thickness is from low to high).Pearly pigment is widely used in the aspects such as paint, ink, coating, plastics, printing-ink, leatheroid, material of construction, makeup, paper, wrapping material, textile printing printing and dyeing, navigation.
But, natural mica has its defect as the body material of pearly pigment: (1) is although can obtain less thickness and larger radius-thickness ratio (general requirement is greater than 50) by the sheet mica that wet milling process is ground and classification obtains, but usually there is wider thickness distribution scope (0.2-1 micron), be easy to the stability affecting plated film like this, not easily the pearly pigment of obtained homogeneous form and aspect; (2) after with metal oxide coated mica sheet, peel off due to mica the aspect stratum and edge gradient thickness that are formed and make light generation scattering phenomenon, reducing pearlescent effect; (3) natural mica contains coloured foreign ion such as iron ion, needs to adopt very numerous and diverse and time-consuming operation steps to remove these foreign ions.
In response to the change of environment and the demand of people's quality of life, pearly pigment can not just be useful in general use as ornamental pigment again, but multi-functional pearly pigment need be had, along with the continuous generation of environmental consciousness rising and more and more many human civilizations disease, therefore product is except the coloured expression power of tool, also in response to possessing the functions such as anti-soil is antibacterial.
Therefore pearly pigment can be prepared into coating further and increase that it is functional, makes it have clean environment power, namely has the function of degradable organic pollutant, resolving harmful gas.Utilize titanium dioxide optical catalyst to carry out environmental purification to have caused and pay attention to widely, the raising of the preparation of titanium dioxide optical catalyst, photocatalytic activity, photocatalyst fixing in also carried out a large amount of research work, because titanium dioxide is a kind of large band gap semi-conductor, TiO 2 particles is excited to need higher energy.Therefore, high photocatalysis efficiency and antimicrobial efficiency be shown, higher to exciting the ultraviolet ray intensity of TiO 2 particles to require.But occurring in nature is very little from the uitraviolet intensity of sunlight.Even if out of doors, ultraviolet ray intensity also can only reach about 1 milliwatt/square centimeter, and indoor ultraviolet ray intensity is just less, and its quantity instrument is microwatt/square centimeter.Therefore, make titanium dioxide optical catalyst in pearly coating, under lower ultraviolet ray intensity, there is the self-cleaning functions such as antibacterial, mildew-resistant, deodorizing, degradable organic pollutant, resolving harmful gas by commercioganic for tool using value.
The coating prepared with pearly pigment also can have effect of anti-bacterial and anti-fouling further, to increase field and the market potential of product application, as namely the paint on wall have the function of dust-proof anti-soil, and long-acting maintenance metope clean and tidy; Or when being applied in the ink of paper, not easily because being infected with of dust makes the expression power of color not good; Also, or can be applicable to wrapping material, during sheathing foodstuff, food not easily causes situation about addling to occur because of microbial growth.
When pearly pigment is prepared into coating and will has other effects in the past, add other antiseptic-germicide or anti-staining agent etc. often and there is the reagent of effect to increase the function of coating, but additive adds the more, then between additive, interrelated factor is then larger, therefore the presenting of effect, more can not display, the mode of this kind of blending can cause pearly pigment cannot show its characteristic and not easily maintain the quality of colour of pearly coating.
In addition, the most widely used market of pearly pigment is exactly makeup, be applied in the makeup on skin, except color expression power must be possessed, the more important thing is to cause skin stimulates and infects, therefore have antibacterial effect and the makeup of gentleness, have again the color expression power of pearly-lustre, be the advantage that makeup should possess simultaneously.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of preparation method of pearly pigment of metallic cover, its pearly pigment has the function of high-efficiency antimicrobial, anti-soil and clean environment power.
For achieving the above object, the present invention provide firstly a kind of preparation method of pearly pigment of metallic cover, its production method comprises the following steps: (1) provides a flat substrates to stir in water to carry out suspension and is heated to 50-80 degree in a nitrogen environment, and regulates the aqueous solution
pHvalue is between 1.5-2.5, and wherein flat substrates can be sheet mica, sheet glass, flake aluminum, sheet pearlstone, aluminium sesquioxide or silicon-dioxide; (2) speed of dripping with 4-10 per second adds titanous chloride aqueous hydrochloric acid, and regulates with aqueous sodium hydroxide solution simultaneously
pHbe worth and maintain between 1.5-2.5, reaction is carried out 8 to 12 hours, and after dropwising, continue stirring 30 minutes under 50-80 degree, titanous chloride is hydrolyzed into titanium sesquioxide and is adsorbed in the sheet structure of mica, forms multiple titanium sesquioxide
receiverice rod is spaced in sheet structure, Ti
2o
3 receiveit is highly 60-80 that rice rod is grown up
receiverice, and there is length for 30-60
receiverice, wide is 30-60
receiverice, and the Ti of multiple columnar interval arrangement
2o
3 receiverice rod, can form a uneven surface in its surface, and have full roughness Rz between 60-80, and can obtain Ti
2o
3coated light blue pearly pigment, if continue reaction further to make Ti
2o
3 receivethe growth of rice rod highly increases, will produce as described in embodiment 1 with every 15
receivemeter Cheng Chang height Sustainable Growth to 500
receiverice, and with gold, red, blue, green circular order, produces the change of different interference color.Preferably situation, Ti
2o
3 receivethe growth of rice rod highly can be 5 ~ 500
receiverice, therefore has full roughness Rz between 5 ~ 500; (3) carry out filtering and washing; (4) dispersing and filtering thing, in water, is heated to 50-80 degree in a nitrogen environment, slowly adds aqueous metal salt and stir 1-3 hour, titanium sesquioxide again
receiverice rod carries out redox reaction with metal-salt, makes Ti
2o
3be oxidized to TiO
2, obtain each titanium dioxide
receiverice rod and flat substrates all deposit multiple metallics, then the TiO of different height of growing up
2colour-change as follows: be 5-80 as degree of growing tall
receivemeter Shi, then become blue by light blue; 80-100
receivemeter Shi, the color of interference then becomes dark gold by gold; Growing up is highly 110
receivemeter Shi, the color of interference is for then to become scarlet by redness; Grow to 125
receivemeter Shi, the color of interference is for then to become mazarine by blueness; Grow to 140
receivemeter Shi, the color of interference then becomes deep green by green, by that analogy, Ti afterwards
2o
3 receiverice rod 2 continues again to grow up, with every 15
receivemeter Cheng Chang height Sustainable Growth to 500
receiverice, then can with gold, red, blue, green circular order, produce the change of different interference color, wherein said metal-salt can be selected from any one or its arbitrary combination in following substances: hydrochloro-auric acid, chlorine molybdic acid, ruthenium chloride, Palladous chloride, rhodium chloride, iron(ic) chloride, Silver Nitrate, cupric nitrate and acid chloride; (5) carry out filtering, washing and drying.
Wherein, described described flat substrates can be commercially available pearly pigment, can be YB103, YB205, YB219, YB300 or YB504 etc., and described commercially available pearly pigment is for base material with any one in sheet mica, sheet glass, flake aluminum, sheet pearlstone, aluminium sesquioxide and silicon-dioxide, wherein, the substrate surface of any one commercially available pearly pigment described is coated with a kind of oxide compound in titanium dioxide, ferric oxide and silicon-dioxide.
Beneficial effect of the present invention: the present invention is multiple
receiverice clavate becomes
receiverice structure has anti-soil, dust-proof effect, and the titanium dioxide formed
receiverice rod also has photocatalysis effect, particularly when silver particles is deposited on titanium dioxide
receivewhen rice rod is upper, can also has further and improve photocatalytic activity and antibacterial effect.
Accompanying drawing explanation
Figure mono-titanium sesquioxide
receivethe schematic diagram of the excellent coated pearly pigment of rice
The schematic diagram of figure bis-metallic cover pearly pigment
500 times of SEM of figure tri-flat substrates distribution scenario look enlarged view
50000 times of SEM of figure tetra-flat substrates surface microstructure look enlarged view
The TEM enlarged section of figure five flat substrates surface microstructure
Embodiment
The invention reside in and a kind of pearly pigment is provided, the wherein flat substrates that uses in pearly pigment, this flat substrates can be natural mica sheet, synthetic mica sheet, sheet glass, flake aluminum, sheet pearlstone, aluminium sesquioxide, silicon-dioxide etc., and the particle diameter of this flat substrates is 2-800 micron, thickness is 0.1-10 micron.In addition, it is emphasized that the present invention is not if prior art is to apply one or more layers titanium dioxide and other metal oxide forms film with enable on base material; And the present invention utilizes to grow multiple column titanium sesquioxide (Ti be spaced on base material
2o
3)
receiverice rod, makes column titanium sesquioxide (Ti
2o
3)
receiverice rod is arranged on base material, and recycles the preparation methods such as speed of reaction, reaction times and pH-value (pH) to control titanium sesquioxide
receivethe growth height of rice rod, uses the color effect determining pearly pigment; Wherein, the present invention forms titanium sesquioxide
receivethe shape of rice rod is close to the crystal formation between cone and right cylinder, but the present invention is not limited
receivethe crystal formation of rice rod; Then, control according to preparation method
receivethe quantity and each that rice clavate becomes
receivethe growth height of rice rod, makes on base material
receivethe account form that rice rod has full roughness Rz, this full roughness Rz is: on flat substrates, get five samples
receivethe average full roughness height of the excellent length of rice, namely gets five column TiO
2 receivethe height that rice is excellent is also averaged, and obtain the value that several mean value can produce a scope, this kind of preparation method makes the reproducibility of pearly pigment Color control improve and can not affect the characteristic of pearly pigment because of base material defectiveness as stated in the Background Art, and makes the Application Areas of this pigment more extensive.
Then, the present invention further provides a kind of pearly pigment of metallic cover, utilize aforementioned preparation process to grow multiple titanium sesquioxide
receiverice rod after the base material of pearly pigment, then adds metal-salt, and to produce redox reaction, make titanium sesquioxide be oxidized to titanium dioxide, metal then reduces and is deposited on the titanium dioxide (TiO of spaced-apart relation
2)
receiverice rod and titanium dioxide (TiO
2)
receiveon the base material of the excellent compartment of rice, now pearly pigment then forms the color of another kind of form and aspect, utilize the deposition results of different metal to change the color of pearly pigment, utilize the light interference effect of metal, make the color of pearly pigment increase the flash effect of another kind of metal.
Further illustrate, work as Ti
2o
3redox becomes TiO
2and metal particle deposition is in TiO
2 receivebehind the excellent surface of rice, its Ti
2o
3 receiverice rod height can because of metallics size some elementary errors distance, in the present invention this slightly gap ignore, therefore, Ti
2o
3 receiveheight after the growth of rice rod can be regarded as and TiO
2 receivethe height of rice rod is identical, and the full roughness Rz numerical value obtained, will with Ti
2o
3 receiverice rod grow up after height and determine, therefore Ti
2o
3 receiverice rod and TiO
2 receivethe full roughness Rz numerical value that rice rod obtains can be regarded as identical.
In a preferred embodiment of the present invention, when reduction is at titanium dioxide
receivewhen metal on rice rod and base material be silver-colored, this pearly pigment then has antibacterial effect, and the major cause with antibacterial effect is, because
receiverice clavate becomes
receiverice structure has full roughness, therefore can be by
receivethe area that the full roughness that rice is excellent increases, makes pearly pigment of the present invention have the argent deposition effect of high area, also therefore improves the antibacterial effect of pearly pigment.The pearly pigment with high antibacterial effect then can be applicable on makeup.In addition, except antibacterial effect, during with monolith substrate, grow up on base material
receiverice clavate becomes
receiverice structure has lotus-effect, make pearly pigment have dust-proof anti-soil effect, dust can be avoided to attach on pigment, cause the skin of health can cause allergy or infection because of dust, and pigment also can be avoided excessively to be attached on skin, cause the situation generation of removing ornaments and formal dress difficult.The germicidal pearlescent cosmetic compositions of tool can be widely used on the preparation of nail polish, lipstick, lip gloss, Mascara, eye shadow or rouge.
In another preferred embodiment of the present invention, also further the pearly pigment with antibacterial and dust-proof antifouling effect can be prepared into coating, a kind of pearly coating with sterilization and dust-proof stain resistance is provided.
And because titanium sesquioxide can form titanium dioxide by oxidation, therefore the speed of reaction in Control release condition, reaction times and pH-value (pH) can be utilized to make titanium sesquioxide be oxidized the titanium dioxide being formed and have photocatalytic activity
receivethe excellent crystal formation of rice, as anatase titanium dioxide, is formed on the base material of pigment, pearly pigment is made to have photocatalysis effect, make pigment have clean environment power, namely there is the function of degradable organic pollutant, resolving harmful gas, and when argent reduction is at titanium dioxide
receiverice rod and base material on after, due to the existence of silver, can further improve photocatalytic activity.
Light-catalysed mechanism is mainly as titanium dioxide (TiO
2) after photocatalyst is subject to being greater than the irradiate light of titanium dioxide energy gap width, in its physical structure, the electrons of valency electricity band is excited to conduction bands, forms unbound electron, and the electronics of valency electricity band will form electric hole, and thus produce electronics-electric hole pair after being stimulated and departing from.Wherein electronics has reductibility, electricity hole has oxidisability, electricity hole can and titanium dioxide surface on the very high hydroxide ion free radical of hydroxide ion reaction generation oxidisability, electrons and oxygen molecule combine and form superoxide ion, active hydroxide ion free radical and superoxide ion can become carbonic acid gas and water organic substance decomposing, and resolving harmful gas, use the effect effectively reaching clean environment.
In addition, titanium dioxide
receiverice rod is formed
receiverice body structure surface, wherein
receivestructure space between rice rod, makes to enter this
receivethe light of rice structure can't produce interference and diffraction, thus reduces the reflection that incident light causes due to refractive index difference, and has antireflection ability, improve photocatalysis effect further.
Therefore also further the pearly pigment with photocatalysis effect can be prepared into coating, a kind of pearly coating with the peace and quiet power of environment is provided.
In addition, the present invention also can utilize commercially available pearly pigment (YB103, YB205, YB219, YB300, YB504 etc.) directly to grow up titanium sesquioxide
receiverice rod is on commercially available pigment, obtain the pigment of different form and aspect color, wherein commercially available pearly pigment can be any one in sheet mica, sheet glass, flake aluminum, sheet pearlstone, aluminium sesquioxide and silicon-dioxide for base material, and the substrate surface of any one commercially available pearly pigment is coated with a kind of oxide compound in titanium dioxide, ferric oxide and silicon-dioxide.
For specifically disclosing and confirming technical characteristic and the effectiveness of pearly pigment of the present invention, following embodiment is proposed in addition to advantage speciality of the present invention as directed.Following embodiment (1-8) is pearly pigment and production method thereof that different structure is described, and the Synthesis and applications of pearly coating.
Embodiment 1: present embodiments provide a kind of pearly pigment, its structure is:
(1) Ti of multiple columnar interval arrangement as shown in figure, is formed on flat substrates 1 surface
2o
3 receiverice rod 2, flat substrates 1 can be natural mica sheet, synthetic mica sheet, sheet glass, flake aluminum, sheet pearlstone, aluminium sesquioxide, silicon-dioxide etc., the particle diameter of flat substrates 1 can be 2-800 micron, thickness can be 0.1-10 micron, the present invention is in the solution utilizing titanous chloride aqueous hydrochloric acid slowly to drop to containing flat substrates 1, make titanous chloride be hydrolyzed into titanium sesquioxide and be adsorbed on flat substrates 1, forming a Ti
2o
3 receiverice rod 2, wherein Ti
2o
3 receiverice rod 2 can according to speed of reaction, reaction times and pH-value (pH value) control Ti
2o
3 receivethe height of rice rod 2, to form the pearly pigment of different colours, namely utilizes Ti
2o
3 receivethe height that rice rod 2 is grown up on the surface at flat substrates is different, and the interference color that flat substrates surface is produced is also just different, and now the form and aspect color that presents of pearly pigment is also just different.In the present embodiment, when Titanium Trichloride Solution drips 8-12 hour, the pH value in reaction process controls at 1.5-2.5, Ti
2o
3 receiveit is highly 60-80 that rice rod 2 is grown up
receiverice, and Ti
2o
3 receivethe length that rice rod 2 is grown up and width are all 30-60
receiverice, makes multiple spaced column Ti
2o
3 receiverice rod 2, can form a uneven surface on the surface at flat substrates 1, and have full roughness Rz between 60-80, and can obtain a light blue pearly pigment; According to Ti
2o
3 receivethe growth height that rice rod 2 is different, its colour-change is as follows: when growing to 5-80
receivemeter Shi is light blue; 80-100
receivemeter Shi, the color of interference is golden; Grow to 110
receivemeter Shi, the color of interference is red; Grow to 125
receivemeter Shi, the color of interference is blue; Grow to 140
receivemeter Shi, the color of interference is green; By that analogy, Ti afterwards
2o
3 receiverice rod 2 continues again to grow up, with every 15
receivemeter Cheng Chang height Sustainable Growth to 500
receiverice, then can with gold, and red, blue, green circular order, produces the change of different interference color.Preferably situation, Ti
2o
3 receivethe growth of rice rod 2 highly can be 5 ~ 500
receiverice, therefore has full roughness Rz between 5 ~ 500.And pearly pigment because surface is formed multiple Ti
2o
3 receiverice rod 2
receiverice structure and have lotus-effect, produces anti-soil and dust-proof effect.
Embodiment 2: the pearly pigment present embodiments providing a kind of metallic cover, its structure is:
(1) as shown in Figure 2, the subsequent step of the embodiment that continues 1, provides another kind of pearly pigment further.(2) Ti on the pearly pigment of embodiment 1 is utilized
2o
3reductibility, after carrying out redox reaction with metal-salt, make Ti
2o
3be oxidized to TiO
2, metallics 4 is reduced and is deposited on TiO
2 receiverice rod 3 and flat substrates on 1; Wherein, metal-salt can be the combination of any one or more of the metal-salts such as hydrochloro-auric acid, chlorine molybdic acid, ruthenium chloride, Palladous chloride, rhodium chloride, iron(ic) chloride, cupric nitrate and acid chloride.Then, TiO is deposited on according to use different metal particle 4
2 receiveon rice rod 3 and flat substrates 1, then can obtaining the coated pearly pigment of different metal, such as, with aqueous solution of chloraurate, after carrying out redox reaction, then can obtaining the coated pearly pigment of the gold of a blueness in addition, when making Ti further
2o
3be oxidized to TiO
2, multiple metal particle deposition is in each titanium dioxide
receivetime on rice rod and flat substrates, then the TiO of different height of growing up
2colour-change as follows: be 5-80 as degree of growing tall
receivemeter Shi, then become blue by light blue; 80-100
receivemeter Shi, the color of interference then becomes dark gold by gold; Growing up is highly 110
receivemeter Shi, the color of interference is for then to become scarlet by redness; Grow to 125
receivemeter Shi, the color of interference is for then to become mazarine by blueness; Grow to 140
receivemeter Shi, the color of interference then becomes deep green by green; By that analogy, TiO afterwards
2 receivethe difference of rice rod is grown up height, with every 15
receivemeter Cheng Chang height Sustainable Growth to 500
receiverice, then can with dark gold, and scarlet, mazarine, bottle-green circular order, produces the change of different interference color.Similarly, the pearly pigment of the present embodiment because surface is formed multiple Ti
2o
3 receiverice rod 2 or TiO
2 receiverice rod 3
receiverice structure and have lotus-effect, produces anti-soil and dust-proof effect.
Embodiment 3: present embodiments provide a kind of pearly pigment, its structure is:
(1) Ti is carried out in its surface with commercially available pearly pigment (YB103, YB205, YB219, YB300, YB504 etc.)
2o
3 receivethe reaction of rice rod is grown up, according to the time for adding control Ti of Titanium Trichloride Solution
2o
3 receivethe growth height of rice rod, carry out reaction after 8 to 12 hours, pH value controls at 1.5-2.5, Ti
2o
3 receiveit is highly 60-80 that rice rod is grown up
receiverice, and there is length for 30-60
receiverice, wide is 30-60
receiverice, and the Ti of multiple columnar interval arrangement
2o
3 receiverice rod, can form a uneven surface in its surface, and have full roughness Rz between 60-80, and can obtain Ti
2o
3coated pearly pigment, and pearly pigment because surface is formed multiple Ti
2o
3 receiverice rod
receiverice structure and have lotus-effect, produces anti-soil and dust-proof effect.
Then, (2) utilize the Ti on commercially available pearly pigment
2o
3reductibility, carry out redox reaction with metal-salt, wherein metal-salt can be the combination of any one or more of the metal-salts such as hydrochloro-auric acid, chlorine molybdic acid, ruthenium chloride, Palladous chloride, rhodium chloride, iron(ic) chloride, cupric nitrate and acid chloride, Ti
2o
3then be oxidized to TiO
2, metallics is then reduced and is deposited on TiO
2 receiverice rod and base material on, utilize the deposition results of different metal to change the color of pearly pigment, utilize the light interference effect of metal, make the color of pearly pigment increase the flash effect of another kind of metal, such as, carry out Ti in its surface with pearly pigment YB103
2o
3 receiveafter the reaction of rice rod is grown up, a light blue pearly pigment can be obtained, after carrying out redox reaction with chlorauric acid solution afterwards, the pearly pigment that the gold of a blueness is coated can be obtained, same, after carrying out redox reaction with other above-mentioned metal-salts, also can obtain a blueness but the pearly pigment that different metal is coated; Or, carry out Ti in its surface with pearly pigment YB205
2o
3 receiveafter the reaction of rice rod is grown up, a golden pearly pigment can be obtained, after carrying out redox reaction with chlorauric acid solution afterwards, the pearly pigment that a dark golden gold is coated can be obtained, same, after carrying out redox reaction with other above-mentioned metal-salts, also can obtain a dark golden but pearly pigment that different metal is coated; Again, Ti is carried out in its surface with pearly pigment YB219
2o
3 receiveafter the reaction of rice rod is grown up, a purple pearly pigment can be obtained, after carrying out redox reaction with chlorauric acid solution afterwards, the pearly pigment that the gold of a purple is coated can be obtained, same, after carrying out redox reaction with other above-mentioned metal-salts, also can obtain a purple but the pearly pigment that different metal is coated; Moreover, carry out Ti in its surface with pearly pigment YB300
2o
3 receiveafter the reaction of rice rod is grown up, a golden pearly pigment can be obtained, after carrying out redox reaction with chlorauric acid solution afterwards, the pearly pigment that the gold of a gold is coated can be obtained, same, after carrying out redox reaction with other above-mentioned metal-salts, also can obtain a gold but the pearly pigment that different metal is coated; In addition, Ti is carried out in its surface with pearly pigment YB504
2o
3 receiveafter the reaction of rice rod is grown up, a brown pearly pigment can be obtained, after carrying out redox reaction with chlorauric acid solution afterwards, the pearly pigment that the gold of a reddish-brown is coated can be obtained, same, after carrying out redox reaction with other above-mentioned metal-salts, also can obtain a reddish-brown but the pearly pigment that different metal is coated.The change of the different interference color that embodiment 3 is illustrated, is all based on Ti
2o
3 receiveit is highly 60-80 that rice rod is grown up
receivewhen rice, if increase Ti more further
2o
3 receiverice rod is grown up highly, then can produce the change of another interference color.In addition, pearly pigment because surface is formed multiple TiO
2 receiverice rod
receiverice structure and have lotus-effect, produces anti-soil and dust-proof effect.
Embodiment 4: present embodiments provide the pearly pigment that Yi Zhong Silver is coated, its structure is:
(1) subsequent step of the embodiment that continues 1, provides another kind of pearly pigment further.(2) Ti on the pearly pigment of embodiment 1 is utilized
2o
3reductibility, carry out redox reaction with metal-salt, wherein metal-salt is Silver Nitrate, Ti
2o
3then be oxidized to TiO
2, argent is then reduced and is deposited on TiO
2 receiverice rod and flat substrates on, now pearly pigment then forms the color of another kind of form and aspect, obtains the pearly pigment that the silver of a blueness is coated, and pearly pigment because surface is formed multiple Ti
2o
3 receiverice rod or TiO
2 receiverice rod
receiverice structure and have lotus-effect, produces anti-soil and dust-proof effect, and has full roughness Rz value, and multiple
receiverice rod is formed again the uneven surface of multiple silver particles, cause the surface-area of silver particles to increase, cause antibacterial effect promoting.
As shown in Figure 3, it is the situation of flat substrates distribution, and the thickness of each plate substrate is about 700
receiverice is between 1 micron; As shown in Figure IV, be the SEM top view of the microtexture on each flat substrates surface in figure tri-; Ti can be found out by figure tetra-
2o
3 receiverice rod becomes TiO through redox
2 receivedistribution scenario after rice rod, forms multiple column TiO
2 receivethe structure of the excellent spaced-apart relation of rice on flat substrates, makes flat substrates form a uneven surface on the surface, and has full roughness Rz between 60-80, and TiO
2 receiveit is 30-60 that rice rod has long
receiverice, wide is 30-60
receiverice, wherein each column TiO
2 receivethe excellent surface of rice also deposits multiple metallics, and its metallics is silver particles, makes flat substrates and each column TiO
2 receiveexcellent surface covers metallics to rice.
As shown in Figure 5, TiO
2 receiverice rod growth height L1 is 60-80
receiverice, and can by each column TiO
2 receivethe excellent surface of rice finds out to have the multiple metallics of deposition, and its metallics is silver particles.
Under one preferred case, full roughness Rz is between 60-80, TiO
2 receiverice rod is right cylinder, and therefore, under the unit surface of one side flat substrates, silver surface is long-pending can increase by 80 ~ 91%, and antibacterial effect can great Fu amplitude be increased.
Except increasing, silver surface is long-pending can be increased except antibacterial effect, and the structural form of antimicrobial surface is (as titanium dioxide
receiverice clavate becomes coarse
receiverice body structure surface) be also one of factor increasing antibacterial effect, utilize TiO
2 receiverice rod between structure space, form a passage, make the silver particles in passage dissociate silver ions time, can discharge by passage, make it produce the silver ions scope of a high local concentrations, there is the effect reducing antibacterial required time.
Embodiment 5: the preparation method present embodiments providing the coated pearly pigment of a kind of argent, its production method comprises the following steps: (particle diameter is 10-60 micron to (1) 60 gram of mica, water-content 33%) stir in 500 ml waters and carry out suspension and be heated to 50-80 degree in a nitrogen environment, and regulate pH value of water solution to equal 1.5-2.5; (2) speed of dripping with 4-10 per second adds 10-20% titanous chloride aqueous hydrochloric acid, and simultaneously maintain pH between 1.5-2.5 with aqueous sodium hydroxide solution adjust ph, reaction is carried out 8 to 12 hours, after dropwising, stirring is continued 30 minutes under 50-80 degree, titanous chloride is hydrolyzed into titanium sesquioxide and is adsorbed in the sheet structure of mica, forms multiple spaced titanium sesquioxide
receiverice is excellent in sheet structure, Ti
2o
3 receiveit is highly 60-80 that rice rod is grown up
receiverice, and there is length for 30-60
receiverice, wide is 30-60
receiverice, and the Ti of multiple columnar interval arrangement
2o
3 receiverice rod, can form a uneven surface in its surface, and have full roughness Rz between 60-80, and can obtain Ti
2o
3coated light blue pearly pigment, if continue reaction further to make Ti
2o
3 receivethe growth of rice rod highly increases, will produce as described in embodiment 1 with gold, red, blue, the circular order of green, the change of generation interference color.Preferably situation, Ti
2o
3 receivethe growth of rice rod 2 highly can be 5 ~ 500
receiverice, therefore has full roughness Rz between 5 ~ 500.And pearly pigment because surface is formed multiple Ti
2o
3 receiverice rod or TiO
2 receiverice rod
receiverice structure and have lotus-effect, produces anti-soil and dust-proof effect; (3) carry out filtering and washing; (4) dispersing and filtering thing, in water, is heated to 50-80 degree in a nitrogen environment again, slowly adds 5-10% (g/ml) 20 milliliters of silver nitrate aqueous solutions and stirs 1-3 hour, titanium sesquioxide
receiverice rod carries out redox reaction with silver nitrate aqueous solution, makes Ti
2o
3be oxidized to TiO
2, obtain each titanium dioxide
receiverice rod and flat substrates all deposit multiple silver particles, then the TiO of different height of growing up
2colour-change as follows: be 5-80 as degree of growing tall
receivemeter Shi, then become blue by light blue; 80-100
receivemeter Shi, the color of interference then becomes dark gold by gold; Growing up is highly 110
receivemeter Shi, the color of interference is for then to become scarlet by redness; Grow to 125
receivemeter Shi, the color of interference is for then to become mazarine by blueness; Grow to 140
receivemeter Shi, the color of interference then becomes deep green by green; By that analogy, TiO afterwards
2 receivethe difference of rice rod is grown up height, with every 15
receivemeter Cheng Chang height Sustainable Growth to 500
receiverice, then can with dark gold, scarlet, mazarine, and bottle-green circular order, produces the change of different interference color; (5) carry out filtering, washing and drying.
Embodiment 6: present embodiments provide a kind of pearly coating with the peace and quiet power of environment, its production method comprises the following steps: (1) continue the subsequent step of embodiment 1, embodiment 2 or embodiment 4, at the multiple TiO of formation
2 receiverice rod
receiveafter the pearly pigment of rice structure,
receiverice structure and TiO
2photocatalysis effect make prepare after pearly coating there is automatically cleaning effect, and pearly pigment because surface is formed multiple TiO
2 receiverice rod
receiverice structure and have lotus-effect, produces anti-soil and dust-proof effect, and multiple because being formed on base material
receiverice rod, makes surface-area increase, even if at lower ultraviolet ray intensity, still can show high photocatalysis effect, and work as TiO
2 receiveafter the upper deposition of rice rod is covered with silver particles, the existence of silver particles then has the effect of promoting photocatalytic activity, makes under visible light, still can have a photocatalysis effect, more promotes the peace and quiet power of environment further.(2) film-forming resin is added and additive is modulated into coating, sample 1 as shown in table 2 proportioning and sample 2, film-forming resin can be epoxy resin, acrylic resin, urethane resin, polycarbonate resin, polyorganosiloxane resin, vinyl polymer resins, polyether resin, aminoplast(ic) resin or vibrin, additive can be any one or more the combination such as film coalescence aid, defoamer, thickening material, dispersion agent, anti-settling agent, flow agent and wetting agent, and dispersion agent comprises polyacrylamide, polycarboxylate, polyethers alcohol amine salt etc.; Film coalescence aid comprises Texanol ester alcohol, LusolvanFBH, Coasol, DBE-IB, DPNB, Dowanol pph etc.; Defoamer comprises silicone antifoam agent, polyether antifoam agent etc.; Thickening material is ether of cellulose and derivative etc. thereof.Importantly pearly pigment is after being prepared into the coating with the peace and quiet power of environment, and the color of coating is deteriorated little, and there is the even look of uniform light on the whole.
And in application aspect, extensively can utilize the doors structure coating, lobby, indoor decoration etc. at material of construction, interior photocatalytic coating can be used for various indoor place, directly be coated on the interior wall substrate surfaces such as plasterboard, timber, wood fibre board, plastics, paint, matrix material, metal, ceramic tile, also can be coated on the furniture surfaces such as floor tile, light fixture, curtain, sanitary china sanitary equipment, produce sterilization, antibacterial and remove the air purification function such as organic pollutant; In addition, also can use out of doors, as the road surface, hard shoulder, edge, roadside, railing etc. of the vehicles such as automobile, bus and outdoor, can effectively absorb and decompose automobile exhaust or the pollution that outdoor environment causes, therefore, will be the application direction of the pollution that the tail gas administering more and more motor vehicle emission causes.
Embodiment 7: present embodiments provide a kind of Zhu Guang Tu with Kill bacterium power and expect, its production method comprises the following steps: (1) continue the subsequent step of embodiment 4, will have silver-colored coated TiO
2 receivethe pearly pigment of rice rod is prepared into coating.(2) add film-forming resin, additive and solvent and be modulated into coating, sample 2 as shown in table 2 proportioning, film-forming resin can be epoxy resin, acrylic resin, urethane resin, polycarbonate resin, polyorganosiloxane resin, vinyl polymer resins, polyether resin, aminoplast(ic) resin or vibrin, additive can be any one or more the combination such as film coalescence aid, defoamer, thickening material, dispersion agent, anti-settling agent, flow agent and wetting agent, and dispersion agent comprises polyacrylamide, polycarboxylate, polyethers alcohol amine salt etc.; Film coalescence aid comprises Texanol ester alcohol, LusolvanFBH, Coasol, DBE-IB, DPNB, Dowanolpph etc.; Defoamer comprises silicone antifoam agent, polyether antifoam agent etc.; Thickening material is ether of cellulose and derivative etc. thereof.Importantly pearly pigment is after being prepared into the germicidal pearly coating of tool, and the color of coating is deteriorated little, and there is the even look of uniform light on the whole, and antibacterial function still has its effect.
Embodiment 8: present embodiments provide the germicidal pearlescent cosmetic compositions of a kind of tool, its production method comprises the following steps: (1) is according to the experimental procedure of embodiment 4, and foundation speed of reaction, reaction times and pH value control TiO
2 receivethe height of rice rod, makes the titanium dioxide of pearly pigment coated difference growth height
receiverice is excellent to form the pearlescent cosmetic compositions of different colours, and at TiO
2 receiverice rod and flat substrates on metal refining silver make its tool antibacterial effect, wherein titanium dioxide
receivethe growth of rice rod highly can be 5 ~ 500
receiverice, and the TiO of different height of growing up
2 receivethe colour-change of rice rod is as follows: be 5-80 as degree of growing tall
receivemeter Shi is then blue; 80-100
receivemeter Shi is then dark golden; Growing up is highly 110
receivemeter Shi is then scarlet; Grow to 125
receivemeter Shi is then mazarine; Grow to 140
receivemeter Shi is then deep green; By that analogy, TiO afterwards
2 receivethe difference of rice rod is grown up height, with every 15
receivemeter Cheng Chang height Sustainable Growth to 500
receiverice, then the color of described pearlescent cosmetic compositions can with dark gold, scarlet, mazarine, bottle-green circular order, produce the change of different interference color, obtain the germicidal pearlescent cosmetic compositions of tool, can be applicable to the preparation of nail polish, lipstick, lip gloss, Mascara, eye shadow or rouge.
The antibacterial test chart of table 1
The formula table of table 2 pearly coating
The photochemical catalysis of table 3 pearly coating and antibacterial test table
1. experimental technique
The experimental technique of table 1 is with reference to " disinfection technology standard (2002 editions) " 2.1.8.3 minimal inhibitory concentration determination test (agar dilution), and experimental strain is intestinal bacteria and staphylococcus aureus.
2. experimental result
Two kinds of bacteriums containing the growing state on the substratum of sample in table 1, sample YB219 adsorbs multiple titanium sesquioxide for utilizing preparation method of the present invention on commercially available pearly pigment
receivethe result of rice rod, sample YB219Ag utilizes the titanium sesquioxide be adsorbed on commercially available pearly pigment
receiverice rod is oxidized to titanium dioxide
receiverice rod, and argent carries out reduction reaction and is deposited on titanium dioxide
receiveresult on rice rod, its antibacterial detected result is:
(1) three concentration of sample YB219 all can suppress intestinal bacteria, to the equal unrestraint effect of staphylococcus aureus.
(2) three concentration of sample YB219Ag all can suppress intestinal bacteria and staphylococcus aureus.
Result shows, and the deposition of high area metal silver on base material, makes the growth that can suppress intestinal bacteria and staphylococcus aureus.
Table 2 is for being made into the formula table of pearly coating, and sample 1 is in coating, add the TiO with photocatalysis effect
2 receivethe pearly pigment that rice rod is coated, sample 2 is in coating, add the TiO with photocatalysis effect
2coated pearly pigment, and at TiO
2deposited on silicon silver particles.
Result shows, and as shown in table 3, the photocatalysis effect of sample 1 (does not add TiO relative to control group
2 receiverice rod), there is the Degradation Formaldehyde rate of 85%, and the carbon monoxide degradation rate of 80%, therefore can learn, prepared by the present invention, there is high surface area TiO
2 receivethe coating that the coated pearly pigment of rice rod is prepared into, has high photocatalysis effect, and can produce the peace and quiet power of environment, therefore can learn, because pearly pigment has multiple TiO on the surface
2 receiverice is excellent and form the flat substrates that high surface area has roughness, even if be prepared into coating, also can not affect its TiO
2 receivethe photocatalysis effect of rice rod; In addition, when further at TiO
2 receiveafter the upper depositing silver particle of rice rod, as sample 2, the existence of silver particles has the effect of promoting photocatalytic activity, makes the Degradation Formaldehyde rate with 93%, and the carbon monoxide degradation rate of 90%, more improves the peace and quiet power of environment further.
Moreover sample 2 is because increase the silver particles deposition of high surface area further, even if by coated for silver TiO
2 receivethe pearly pigment of rice rod is prepared into coating, and sample 2 has antibacterial effect too and can suppress intestinal bacteria and staphylococcus aureus.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for the pearly pigment of metallic cover, comprises the following steps: (1) provides a flat substrates to stir in water to carry out suspension and heats in a nitrogen environment, regulates pH value of water solution between 1.5-2.5; (2) titanous chloride aqueous hydrochloric acid is provided and adds in the mode progressively instilled, and also maintain between 1.5-2.5 with aqueous sodium hydroxide solution adjust ph simultaneously, described titanous chloride is hydrolyzed into titanium sesquioxide and is adsorbed on described flat substrates, and the nanometer rod of the multiple titanium sesquioxides described in formation is spaced on described flat substrates; (3) carry out filtering and washing, obtain a filtrate; (4) again disperse described filtrate in water, heat in a nitrogen environment, slowly add aqueous metal salt and stir, described titanium sesquioxide nanometer rod and described metal-salt carry out redox reaction, make described titanium sesquioxide nanometer rod be oxidized to titanium dioxide nano-rod, obtain each described titanium dioxide nano-rod and described flat substrates all deposit multiple silver particles; (5) carry out filtering, washing and drying.
2. the preparation method of the pearly pigment of metallic cover according to claim 1, described hydrolysising reacting temperature is 50-80 degree.
3. the preparation method of the pearly pigment of metallic cover according to claim 1, described hydrolysis time is 8 to 12 hours.
4. the preparation method of the pearly pigment of metallic cover according to claim 3, the height of described titanium sesquioxide nanometer rod is 60-80 nanometer.
5. the preparation method of the pearly pigment of metallic cover according to claim 1, the speed of described titanous chloride aqueous hydrochloric acid instillation is that 4-10 per second drips.
6. the preparation method of the pearly pigment of metallic cover according to claim 1, described redox reaction temperature is 50-80 degree.
7. the preparation method of the pearly pigment of metallic cover according to claim 1, the described redox reaction time is 1-3 hour.
8. the preparation method of the pearly pigment of metallic cover according to claim 1, described metal-salt is Silver Nitrate.
9. the preparation method of the pearly pigment of metallic cover according to claim 1, described flat substrates is any one in sheet mica, sheet glass, aluminium sesquioxide, flake aluminum, sheet pearlstone and silicon-dioxide.
10. the preparation method of the pearly pigment of metallic cover according to claim 1, described flat substrates is a commercially available pearly pigment, described commercially available pearly pigment is for base material with any one in sheet mica, sheet glass, flake aluminum, sheet pearlstone, aluminium sesquioxide and silicon-dioxide, wherein, the substrate surface of any one commercially available pearly pigment described is coated with a kind of oxide compound in titanium dioxide, ferric oxide and silicon-dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410052460.9A CN103788720B (en) | 2014-02-17 | 2014-02-17 | Method for preparing metal coated pearlescent pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410052460.9A CN103788720B (en) | 2014-02-17 | 2014-02-17 | Method for preparing metal coated pearlescent pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103788720A CN103788720A (en) | 2014-05-14 |
| CN103788720B true CN103788720B (en) | 2015-05-20 |
Family
ID=50664799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410052460.9A Active CN103788720B (en) | 2014-02-17 | 2014-02-17 | Method for preparing metal coated pearlescent pigment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103788720B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106444139A (en) * | 2016-11-02 | 2017-02-22 | 深圳市盛波光电科技有限公司 | Method for controlling visual effect of semi-transparent semi-reflective polarizer |
| WO2018096936A1 (en) * | 2016-11-25 | 2018-05-31 | 日本板硝子株式会社 | Lustrous pigment, pigment-containing composition, and pigment-containing coated article |
| CN116478560A (en) * | 2023-03-24 | 2023-07-25 | 瑞彩科技股份有限公司 | Black pearlescent pigment and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0905205A2 (en) * | 1997-09-30 | 1999-03-31 | Shiseido Company Limited | Coloured titanium dioxide coated mica pigment and article coated using the same |
-
2014
- 2014-02-17 CN CN201410052460.9A patent/CN103788720B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0905205A2 (en) * | 1997-09-30 | 1999-03-31 | Shiseido Company Limited | Coloured titanium dioxide coated mica pigment and article coated using the same |
| CN1216772A (en) * | 1997-09-30 | 1999-05-19 | 株式会社资生堂 | Color titanium dioxide coated mica pigment and coated-body using the same |
| US6129784A (en) * | 1997-09-30 | 2000-10-10 | Shiseido Co., Ltd. | Color titanated mica pigment and coated-body using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103788720A (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhong et al. | TiO2/silane coupling agent composed of two layers structure: A super-hydrophilic self-cleaning coating applied in PV panels | |
| CN1563210A (en) | Pigment changed color as changing angle, and fabricating method | |
| Wang et al. | Self-cleaning and depollution of fiber reinforced cement materials modified by neutral TiO2/SiO2 hydrosol photoactive coatings | |
| CN101525504A (en) | Photocatalytic self-cleaning film coating agent with self-layered isolation effect and preparation method thereof | |
| CN103788720B (en) | Method for preparing metal coated pearlescent pigment | |
| JP2003291243A (en) | Method for cleaning surface of base material, base material having cleaning surface, and cleaning coating composition | |
| CN103131313A (en) | Compound type photocatalyst air purification waterborne interior wall coating and preparation method thereof | |
| JP4619601B2 (en) | PHOTOCATALYTIC COATING COMPOSITION AND PRODUCT HAVING PHOTOCATALYTIC THIN FILM | |
| KR20120078637A (en) | Coating composition and uses thereof | |
| CN103464129A (en) | Lanthanum doped nano TiO2/tourmaline composite, and preparation and application of composite | |
| CN108467646A (en) | A kind of automatically cleaning energy-saving coatings as well as preparation method and application thereof with air-cleaning function | |
| Bianchi et al. | A new frontier of photocatalysis employing micro-sized TiO2: Air/water pollution abatement and self-cleaning/antibacterial applications | |
| CN102821850A (en) | Photocatalyst-coated body and photocatalyst coating liquid | |
| Taga | Titanium oxide based visible light photocatalysts: Materials design and applications | |
| CN103923501B (en) | A kind of Nano sol for the formation of anti-aging, stain resistant nano coating and preparation method and application | |
| CN103788722B (en) | Pearlescent pigment with bactericidal power | |
| JP3598274B2 (en) | Coating solution for photocatalytic film containing organic dye | |
| CN101139473A (en) | Nano inner-exterior wall emulsion paint and preparation method thereof | |
| CN1384152A (en) | Titania nano-paint for photocatalytic decomposition of organic matter and its prepn | |
| JP4738736B2 (en) | Photocatalyst composite, coating solution for forming photocatalyst layer, and photocatalyst carrying structure | |
| CN103788721B (en) | A kind of pearly pigment of metallic cover | |
| CN104893375A (en) | Organic-inorganic hybrid photocatalysis top coating as well as preparation method and application thereof | |
| CN103804976A (en) | Pearlescent pigment with environment cleaning capacity | |
| Toniolo et al. | The protection of marble surfaces: The challenge to develop suitable nanostructured treatments | |
| CN103784334B (en) | A kind of have germicidal pearlescent cosmetic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 200060 Fengshan Section of Kunao Avenue, Pingyang Economic Development Zone, Wenzhou City, Zhejiang Province Co-patentee after: SHANGHAI YIBAI CHEMICAL CO., LTD. Patentee after: Zhejiang Ruicheng New Materials Co., Ltd. Address before: 200060 Fengshan Section of Kunao Avenue, Pingyang Economic Development Zone, Wenzhou City, Zhejiang Province Co-patentee before: SHANGHAI YIBAI CHEMICAL CO., LTD. Patentee before: Zhejiang Ruicheng Effect Pigment Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200114 Address after: 325401 Fengshan Section of Kunao Avenue, Pingyang Economic Development Zone, Wenzhou City, Zhejiang Province Patentee after: Zhejiang Ruicheng New Materials Co., Ltd. Address before: 200060 Fengshan section, Kun Ao Road, Pingyang Economic Development Zone, Wenzhou, Zhejiang Co-patentee before: SHANGHAI YIBAI CHEMICAL CO., LTD. Patentee before: Zhejiang Ruicheng New Materials Co., Ltd. |