CN103788722A - Pearlescent pigment with bactericidal power - Google Patents
Pearlescent pigment with bactericidal power Download PDFInfo
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- CN103788722A CN103788722A CN201410052685.4A CN201410052685A CN103788722A CN 103788722 A CN103788722 A CN 103788722A CN 201410052685 A CN201410052685 A CN 201410052685A CN 103788722 A CN103788722 A CN 103788722A
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- pearly pigment
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Abstract
The invention discloses a pearlescent pigment with bactericidal power. The pearlescent pigment is characterized by comprising a flaky substrate, film forming resin 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 silver 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 metallic cover powder pigment, relate in particular to the germicidal metallic cover pearly pigment of a kind of tool.
Background technology
Pearly pigment has the pigment of giving gloss as goods pearl, it is take transparent or translucent thin slice as core, adopt the film of special chemical technology in its coated one or more layers titanium dioxide in surface and the formation of other metal oxide, in the time that irradiate light arrives pearly pigment interface, can produce reflected light and refracted light, after the transmission of part light, reflect again, 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 high refraction in outside, in the time that being irradiated on the pigment of this type, white light reflected by titanium dioxide layer segment, remaining light arrives at mica surface through (refraction) titanium dioxide layer, then part light is reflected again, is parallel to first reflection ray and leaves surface of pigments.The light wave of second light relatively has part with first light and is offset, according to the length difference of institute's route via, bias size difference.If crest and crest stack, trough and trough stack, will strengthen light wave.By apply the titanium dioxide of different thickness on mica, can obtain from silvery white, through yellow, redness, blueness, 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 conventionally there is wider thickness distribution scope (0.2-1 micron), be easy to like this affect the stability of plated film, be difficult for making the pearly pigment of homogeneous form and aspect; (2) when being coated after sheet mica with metal oxide, aspect stratum and the edge gradient thickness of peeling off formation due to mica make light generation scattering phenomenon, have reduced pearlescent effect; (3) natural mica contains coloured foreign ions 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 need there is multi-functional pearly pigment, along with environmental consciousness rising and the more and more continuous generation of 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 further can be prepared into coating 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 and caused attention widely, aspect the raising of the preparation of titanium dioxide optical catalyst, photocatalytic activity, photocatalyst fixing, also carry out a large amount of research work, because titanium dioxide is a kind of large band gap semi-conductor, excite TiO 2 particles to need higher energy.Therefore, show high photocatalysis efficiency and antimicrobial efficiency, the ultraviolet ray intensity that excites TiO 2 particles is had relatively high expectations.But occurring in nature is very little from the uitraviolet intensity of sunlight.Even out of doors, ultraviolet ray intensity also can only reach 1 milliwatt/square centimeter left and right, 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 tool using value.
The coating of preparing with pearly pigment further also can have effect of anti-bacterial and anti-fouling, to increase field and the market potential of product application, and as the paint on wall have the function of dustproof anti-soil, long-acting maintenance metope clean and tidy; Or while being applied in the ink of paper, be difficult for making the expression power of color not good because of being infected with of dust; Also or can be applicable to wrapping material,, when sheathing foodstuff, food is difficult for occurring because microbial growth causes situation about addling.
When pearly pigment is prepared into coating and will has other effects in the past, add reagent that other antiseptic-germicides or anti-staining agent etc. have effect beyond tending to increase the function of coating, but additive adds the more, between additive, interrelated factor is larger, therefore presenting of effect more can not display, and the mode of this kind of blending can cause pearly pigment cannot show its characteristic and be difficult for maintaining 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 possessing color expression power, the more important thing is and can not cause and stimulate and infect skin, therefore having antibacterial effect and gentle makeup, have again the color expression power of pearly-lustre simultaneously, is the advantage that makeup should possess.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide the germicidal pearly coating of a kind of tool, its pearly coating has the function of high-efficiency antimicrobial, anti-soil and clean environment power.
For achieving the above object, first the present invention provides a kind of tool germicidal pearly coating, its pearly coating comprises a flat substrates and a film-forming resin, how rice is excellent on its flat substrates surface, to be covered with multiple spaced titanium dioxide, how each titanium dioxide all deposit multiple silver particles on rice rod and flat substrates, form multiple titanium dioxide how rice rod how rice structure and there is lotus-effect, produce anti-soil and dustproof effect.
Wherein, described 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 flat substrates is 2-800 micron, and thickness is 0.1-10 micron.
Wherein, described 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 etc.
Wherein, described flat substrates has full roughness Rz (DIN) between 5～500.
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 take any in sheet mica, sheet glass, flake aluminum, sheet pearlstone, aluminium sesquioxide and silicon-dioxide as base material, wherein, the substrate surface of described any commercially available pearly pigment is coated with a kind of oxide compound in titanium dioxide, ferric oxide and silicon-dioxide.
Beneficial effect of the present invention: the how rice structure that the multiple how rice of the present invention clavate becomes has anti-soil, dustproof effect, and how rice rod also has photocatalysis effect to the titanium dioxide forming, particularly, in the time that silver particles is deposited on titanium dioxide how rice rod is upper, can also further there is the photocatalytic activity of raising and antibacterial effect.
Accompanying drawing explanation
Fig. 1 titanium sesquioxide is the schematic diagram of the coated pearly pigment of rice rod how
The schematic diagram of Fig. 2 metallic cover pearly pigment
On 500 times of SEM of Fig. 3 flat substrates distribution scenario, look enlarged view
On 50000 times of SEM of Fig. 4 flat substrates surface microstructure, look enlarged view
The TEM cross section enlarged view of Fig. 5 flat substrates surface microstructure
Embodiment
The invention reside in a kind of pearly pigment is provided, what wherein in pearly pigment, use is flat substrates, 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, be stressed that, the present invention is not if prior art is to apply one or more layers titanium dioxide and other metal oxide to enable forming film on base material; And the present invention is the column titanium sesquioxide (Ti that utilizes multiple each intervals of growing on base material
2o
3) how rice is excellent, makes column titanium sesquioxide (Ti
2o
3) how a rice rod be arranged on base material, and recycle the preparation methods such as speed of reaction, reaction times and pH-value (pH) and control the how growth height of rice rod of titanium sesquioxide, use the color effect that determines pearly pigment; Wherein, titanium sesquioxide that the present invention forms a how shape for rice rod is the crystal formation approaching between cone and right cylinder, but how the present invention limit the excellent crystal formation of rice; Then, control the growth height of quantity that how rice clavate becomes and each how rice rod according to preparation method, make the how rice rod on base material there is a full roughness Rz (DIN), the account form of this full roughness Rz (DIN) is: on flat substrates, get the average full roughness height of the excellent length of how rice of five samples, namely get five column TiO
2how the height of rice rod averaging, and obtain several mean value and can produce the value of a scope, this kind of preparation method makes the reproducibility of pearly pigment color control improve and can not affect because of base material defectiveness as stated in the Background Art the characteristic of pearly pigment, and makes the Application Areas of this pigment more extensive.
Then, the present invention further provides a kind of pearly pigment of metallic cover, how rice rod is after the base material of pearly pigment for multiple titanium sesquioxides to utilize aforementioned preparation method to grow, add again metal-salt, to produce redox reaction, make titanium sesquioxide be oxidized to titanium dioxide, metal reduce and be deposited on each interval arrange titanium dioxide (TiO
2) how rice rod and titanium dioxide (TiO
2) how on the base material of the excellent compartment of rice, now pearly pigment 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 metallics is deposited on TiO
2how behind the excellent surface of rice, its Ti
2o
3how the height of rice rod can be because of some elementary errors distance of metallics size, in the present invention this slightly gap ignore, therefore, Ti
2o
3how the height of rice rod after growing up can be regarded as and TiO
2how meter excellent height is identical, and full roughness Rz (DIN) numerical value obtaining, will be with Ti
2o
3how the height of rice rod after growing up and determine therefore Ti
2o
3how rice rod and TiO
2full roughness Rz (DIN) numerical value how rice rod obtains can be regarded as identical.
In a preferred embodiment of the present invention, when reduction is at titanium dioxide when how the metal on rice rod and base material be silver-colored, this pearly pigment has antibacterial effect, and the major cause with antibacterial effect is, because how rice clavate become how a rice structure has full roughness, therefore can by how the area that increases of the full roughness of rice rod, make pearly pigment of the present invention there is the argent deposition effect of high area, also therefore improved the antibacterial effect of pearly pigment.The pearly pigment with high antibacterial effect can be applicable on makeup.In addition, except antibacterial effect, during with monolith substrate, how the rice clavate of growing up on base material become how a rice structure has lotus-effect, make pearly pigment there is dustproof anti-soil effect, can avoid dust to attach on pigment, cause the skin of health to cause allergy or infection because of dust, and also can avoid pigment to be excessively attached on skin, cause the situation of removing ornaments and formal dress difficult to occur.The germicidal pearly-lustre make-up composition of tool can be widely used on the preparation of nail lustering agent, lipstick, lip gloss, Mascara, eye shadow or rouge.
In another preferred embodiment of the present invention, also can further the pearly pigment with antibacterial and dustproof anti-soil effect be prepared into coating, a kind of pearly coating with sterilization and dustproof stain resistance is provided.
And because titanium sesquioxide can form titanium dioxide by oxidation, therefore can utilize the speed of reaction of controlling in experiment condition, reaction times and pH-value (pH) form titanium sesquioxide oxidation to have the how excellent crystal formation of rice of titanium dioxide of photocatalytic activity, as anatase titanium dioxide, be formed on the base material of pigment, make pearly pigment can there is photocatalysis effect, make pigment there is clean environment power, namely there is degradable organic pollutant, the function of resolving harmful gas, and when argent reduction is after titanium dioxide is how on rice rod and base material, due to silver-colored existence, can further improve photocatalytic activity.
Light-catalysed mechanism is mainly as titanium dioxide (TiO
2) photocatalyst is subject to being greater than after 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 after being stimulated and departing from, thereby generation electronics-electric hole pair.Wherein electronics has reductibility, electricity hole has oxidisability, hydroxide ion reaction on the meeting of electricity hole and titanium dioxide surface generates the very high hydroxide ion free radical of oxidisability, electrons and oxygen molecule are in conjunction with forming 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 that effectively reaches clean environment.
In addition, the titanium dioxide how rice body structure surface how rice rod forms, the wherein structure space between rice rod how, the light that makes to enter this how rice structure can't produce interferes and diffraction, thereby reduce the reflection that incident light causes due to refractive index difference, and there is antireflection ability, further promote photocatalysis effect.
Therefore also can further the pearly pigment with photocatalysis effect 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, and how rice rod is on commercially available pigment for titanium sesquioxide, obtain the pigment of different form and aspect colors, wherein commercially available pearly pigment can be any in sheet mica, sheet glass, flake aluminum, sheet pearlstone, aluminium sesquioxide and silicon-dioxide for base material, and the substrate surface of any commercially available pearly pigment is coated with a kind of oxide compound in titanium dioxide, ferric oxide and silicon-dioxide.
For specifically disclosing and confirm technical characterictic 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 the production method thereof of explanation different structure, and the preparation of pearly coating and application.
Embodiment 1: the present embodiment Ti Gong ー kind pearly pigment, its structure is:
(1) as shown in Figure 1, form on flat substrates 1 surface the Ti that multiple columnar intervals are arranged
2o
3how rice 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 utilizes titanous chloride aqueous hydrochloric acid slowly to drop in the solution that contains flat substrates 1, make titanous chloride be hydrolyzed into titanium sesquioxide and be adsorbed on flat substrates 1, forming a Ti
2o
3how rice rod 2, wherein Ti
2o
3how rice rod 2 can be controlled Ti according to speed of reaction, reaction times and pH-value (pH value)
2o
3how the height of rice rod 2, to form the pearly pigment of different colours, namely utilizes Ti
2o
3how the rice rod 2 height differences of growing up on flat substrates surface, the interference color that flat substrates surface is produced is also just different, and the form and aspect color that now pearly pigment presents is also just different.In the present embodiment, when Titanium Trichloride Solution drips 8-12 hour, the pH value in reaction process is controlled at 1.5-2.5, Ti
2o
3how rice rod 2 grow up be highly 60-80 how meter, and Ti
2o
3how the length that rice rod 2 is grown up and width are all how rice of 30-60, make multiple spaced column Ti
2o
3how rice rod 2 can form a uneven surface, and have full roughness Rz (DIN) between 60-80, and can obtain a light blue pearly pigment on flat substrates 1 surface; According to Ti
2o
3how the different growth height of rice rod 2, its colour-change is as follows: when growing to 5-80 how when rice, be all light blue; 80-100 is how when rice, and the color of interference be gold; Grow to 110 how when rice, the color of interference be redness; Grow to 125 how when rice, the color of interference be blueness; Grow to 140 how when rice, the color of interference be green; By that analogy, Ti afterwards
2o
3how rice rod 2 continues again to grow up, with every 15 how rice of meter Cheng Chang height Sustainable Growth to 500 how, can be with gold, and redness, blueness, green circular order, the variation that produces different interference color.Preferably situation, Ti
2o
3how the growth of rice rod 2 highly can be 5～500 rice how, therefore has full roughness Rz (DIN) between 5～500.And pearly pigment is multiple Ti because surface forms
2o
3how the how rice structure of rice rod 2 and have lotus-effect, produces anti-soil and dustproof effect.
Embodiment 2: the pearly pigment of the present embodiment Ti Gong ー kind metallic cover, its structure is:
(1) as shown in Figure 2, the subsequent step of the embodiment 1 that continues, further provides another kind of pearly pigment.(2) utilize the Ti on the pearly pigment of embodiment 1
2o
3reductibility, carry out, after redox reaction, making Ti with metal-salt
2o
3be oxidized to TiO
2, 4 of metallicss are reduced and are deposited on TiO
2how on rice rod 3 and flat substrates 1; Wherein, metal-salt can be any one or more combination 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, according to using different metal particle 4 to be deposited on TiO
2how on rice rod 3 and flat substrates 1, can obtain the coated pearly pigment of different metal, for example, with aqueous solution of chloraurate, carry out after redox reaction, can obtain the coated pearly pigment of gold of a blueness, in addition, when carrying out after redox reaction with other metal-salts, can obtain a same color but the coated pearly pigment of different metal, when utilizing Ti
2o
3how the rice rod 2 height differences of growing up on pearly pigment surface, the interference color that pearly pigment surface produces just can be different, also difference (as described in Example 1) just of the form and aspect color that now pearly pigment presents; In addition, when further making Ti
2o
3be oxidized to TiO
2, multiple metallicss are deposited on each titanium dioxide how on rice rod and flat substrates time, the TiO of the different height of growing up
2colour-change as follows: be that 5-80 is how when rice, by the light blue blueness that becomes as degree of growing tall; 80-100 is how when rice, and the color of interference becomes dark gold by gold; How meter grow up is highly 110 time, and the color of interference is for becoming scarlet by redness; Grow to 125 how when rice, the color of interference is for becoming mazarine by blueness; Grow to 140 how when rice, the color of interference becomes deep green by green; By that analogy, TiO afterwards
2how a difference for rice rod the height of growing up, with every 15 how rice of meter Cheng Chang height Sustainable Growth to 500 how, can be with dark gold, scarlet, mazarine, bottle-green circular order, the variation that produces different interference color.Similarly, the pearly pigment of the present embodiment because surface forms multiple Ti
2o
3how rice rod 2 or TiO
2how the how rice structure of rice rod 3 and have lotus-effect, produces anti-soil and dustproof effect.
Embodiment 3: the present embodiment Ti Gong ー kind pearly pigment, its structure is:
(1) carry out in its surface Ti with commercially available pearly pigment (YB103, YB205, YB219, YB300, YB504 etc.)
2o
3how the reaction of rice rod is grown up, and controls Ti according to the time for adding of Titanium Trichloride Solution
2o
3how meter excellent growth highly, is reacted after 8 to 12 hours, and pH value is controlled at 1.5-2.5, Ti
2o
3how to grow up be highly how rice of 60-80 to rice rod, and to have long be how rice of 30-60, wide be 30-60 how meter, and the Ti of multiple columnar interval arrangement
2o
3how rice is excellent, can form in its surface a uneven surface, and have full roughness Rz (DIN) between 60-80, and can obtain Ti
2o
3coated pearly pigment, and pearly pigment because surface forms multiple Ti
2o
3how the how rice structure of rice rod and have lotus-effect, produces anti-soil and dustproof 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 any one or more combination 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
3be oxidized to TiO
2, metallics is reduced and is deposited on TiO
2how on rice rod and base material, 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, for example, carry out in its surface Ti with pearly pigment YB103
2o
3how rice rod reacts after growth, can obtain a light blue pearly pigment, carry out after redox reaction with chlorauric acid solution afterwards, can obtain the coated pearly pigment of gold of a blueness, same, carry out after redox reaction with other above-mentioned metal-salts, also can obtain a blueness but the coated pearly pigment of different metal; Or, carry out in its surface Ti with pearly pigment YB205
2o
3how rice rod reacts after growth, can obtain a golden pearly pigment, carry out after redox reaction with chlorauric acid solution afterwards, can obtain a dark golden coated pearly pigment of gold, same, carry out after redox reaction with other above-mentioned metal-salts, also can obtain a dark golden but coated pearly pigment of different metal; Carry out in its surface Ti with pearly pigment YB219 again,
2o
3how rice rod reacts after growth, can obtain a purple pearly pigment, carry out after redox reaction with chlorauric acid solution afterwards, can obtain the coated pearly pigment of gold of a purple, same, carry out after redox reaction with other above-mentioned metal-salts, also can obtain a purple but the coated pearly pigment of different metal; Moreover, carry out in its surface Ti with pearly pigment YB300
2o
3how rice rod reacts after growth, can obtain a golden pearly pigment, carry out after redox reaction with chlorauric acid solution afterwards, can obtain the coated pearly pigment of gold of a gold, same, carry out after redox reaction with other above-mentioned metal-salts, also can obtain a gold but the coated pearly pigment of different metal; In addition, carry out in its surface Ti with pearly pigment YB504
2o
3how rice rod reacts after growth, can obtain a brown pearly pigment, carry out after redox reaction with chlorauric acid solution afterwards, can obtain the coated pearly pigment of gold of a reddish-brown, same, carry out after redox reaction with other above-mentioned metal-salts, also can obtain a reddish-brown but the coated pearly pigment of different metal.The variation of the different interference color that embodiment 3 gives an example, is all based on Ti
2o
3how how meter grow up be highly in 60-80 situation, if further increase Ti to rice rod again
2o
3how rice rod is grown up highly, the variation that can produce another interference color.In addition, pearly pigment because surface forms multiple TiO
2how the how rice structure of rice rod and have lotus-effect, produces anti-soil and dustproof effect.
Embodiment 4: the coated pearly pigment of the present embodiment Ti Gong ー Zhong Silver, its structure is:
(1) the continue subsequent step of embodiment 1, further provides another kind of pearly pigment.(2) utilize the Ti on the pearly pigment of embodiment 1
2o
3reductibility, carry out redox reaction with metal-salt, wherein metal-salt is Silver Nitrate, Ti
2o
3be oxidized to TiO
2, argent is reduced and is deposited on TiO
2how on rice rod and flat substrates, now pearly pigment forms the color of another kind of form and aspect, obtains the coated pearly pigment of silver of a blueness, and pearly pigment because surface forms multiple Ti
2o
3how rice rod or TiO
2how the how rice structure of rice rod and there is lotus-effect, produce anti-soil and dustproof effect, and there is full roughness Rz (DIN) value, and on multiple how meter rod, form 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 that flat substrates distributes, the thickness of each plate substrate be about 700 how rice between 1 micron; As shown in Figure 4, be the SEM top view of the lip-deep microtexture of each flat substrates in Fig. 3; Ti as seen from Figure 4
2o
3how rice rod becomes TiO through redox
2how the distribution scenario after rice rod, forms multiple column TiO
2how the excellent each interval of rice is arranged in the structure on flat substrates, and make to form on flat substrates surface a uneven surface, and there is full roughness Rz (DIN) between 60-80, and TiO
2how to have long be how rice of 30-60 to a rice rod, wide be 30-60 how meter, wherein each column TiO
2how the excellent surface of rice also deposits multiple metallicss, and its metallics is silver particles, makes flat substrates and each column TiO
2how on the excellent surface of rice, covered metallics.
As shown in Figure 5, TiO
2how the rice rod height L1 that grows up is how rice of 60-80, and can be by each column TiO
2how the excellent surface of rice is found out has the multiple metallicss of deposition, and its metallics is silver particles.
Under one preferred case, full roughness Rz (DIN) is between 60-80, TiO
2how rice 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 antibacterial effect, the structural form of antimicrobial surface (as titanium dioxide how rice clavate become coarse how rice body structure surface) be also one of factor increasing antibacterial effect, utilize TiO
2how the structure space between rice rod, forms a passage, while making silver particles in passage dissociate silver ions, can discharge by passage, makes its silver ions scope that produces a high local concentrations, has the effect that reduces antibacterial required time.
Embodiment 5: the preparation method of the coated pearly pigment of the present embodiment Ti Gong ー kind argent, its production method comprises the following steps: (particle diameter is 10-60 micron to (1) 60 gram of mica, water-content 33%) in 500 ml waters, stir and suspend and under nitrogen environment, be heated to 50-80 degree, 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 regulate pH value and maintain pH between 1.5-2.5 with aqueous sodium hydroxide solution simultaneously, reaction is carried out 8 to 12 hours, after dropwising, under 50-80 degree, continue to stir 30 minutes, titanous chloride is hydrolyzed into titanium sesquioxide and is adsorbed in the sheet structure of mica, forms the how rice rod of multiple spaced titanium sesquioxides in sheet structure, Ti
2o
3how to grow up be highly how rice of 60-80 to rice rod, and to have long be how rice of 30-60, wide be 30-60 how meter, and the Ti of multiple columnar interval arrangement
2o
3how rice is excellent, can form in its surface a uneven surface, and have full roughness Rz (DIN) between 60-80, and can obtain Ti
2o
3coated light blue pearly pigment, makes Ti if further continue reaction
2o
3how a growth for rice rod highly increases, will produce as described in embodiment 1 with gold, redness, blueness, the circular order of green, the variation of generation interference color.Preferably situation, Ti
2o
3how the growth of rice rod 2 highly can be 5～500 rice how, therefore has full roughness Rz (DIN) between 5～500.And pearly pigment is multiple Ti because surface forms
2o
3how rice rod or TiO
2how the how rice structure of rice rod and have lotus-effect, produces anti-soil and dustproof effect; (3) filter and wash; (4) again dispersing and filtering thing to water, under nitrogen environment, be heated to 50-80 degree, slowly add 20 milliliters of silver nitrate aqueous solutions of 5-10% (g/ml) and stir 1-3 hour, how rice rod carries out redox reaction with silver nitrate aqueous solution to titanium sesquioxide, makes Ti
2o
3be oxidized to TiO
2, obtain each titanium dioxide and how on rice rod and flat substrates, all deposit multiple silver particles, the TiO of the different height of growing up
2colour-change as follows: be that 5-80 is how when rice, by the light blue blueness that becomes as degree of growing tall; 80-100 is how when rice, and the color of interference becomes dark gold by gold; How meter grow up is highly 110 time, and the color of interference is for becoming scarlet by redness; Grow to 125 how when rice, the color of interference is for becoming mazarine by blueness; Grow to 140 how when rice, the color of interference becomes deep green by green; By that analogy, TiO afterwards
2how a difference for rice rod the height of growing up, with every 15 how rice of meter Cheng Chang height Sustainable Growth to 500 how, can be with dark gold, scarlet, mazarine, bottle-green circular order, the variation that produces different interference color; (5) filter, wash and be dried.
Embodiment 6: the present embodiment Ti Gong ー kind has the pearly coating of the peace and quiet power of environment, and its production method comprises the following steps: (1) continue subsequent step of embodiment 1, embodiment 2 or embodiment 4, is forming multiple TiO
2how after the pearly pigment of the how rice structure of rice rod, how rice structure and TiO
2photocatalysis effect make preparation after pearly coating there is automatically cleaning effect, and pearly pigment because surface forms multiple TiO
2how the how rice structure of rice rod and have lotus-effect, produces anti-soil and dustproof effect, and because form multiple how rice rods on base material, makes surface-area increase, even at lower ultraviolet ray intensity, still can show high photocatalysis effect, and work as TiO
2how the upper deposition of rice rod is covered with after silver particles, and the existence of silver particles has the effect of promoting photocatalytic activity, makes under visible ray, still can have a photocatalysis effect, further more promotes the peace and quiet power of environment.(2) add film-forming resin and additive to be 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 combinations 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 thereof etc.Importantly pearly pigment is being prepared into after the coating with the peace and quiet power of environment, and the color variation of coating is little, and has on the whole the even look of uniform light.
And in application aspect, can extensively utilize at the doors structure coating of material of construction, booth platform, indoor decoration etc., interior photocatalytic coating can be used for various indoor places, 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 vehicles such as automobile, bus and outdoor road surface, hard shoulder, edge, roadside, railing etc., can effectively absorb and decompose automobile exhaust or the pollution that outdoor environment causes, the application direction of the pollution therefore, the tail gas that is the more and more motor vehicle emissions of improvement being caused.
Embodiment 7: the present embodiment Ti Gong ー kind has the Zhu Guang Tu material of Kill bacterium power, and its production method comprises the following steps: (1) continue subsequent step of embodiment 4, will have silver and be coated TiO
2how the excellent pearly pigment of rice is prepared into coating.(2) add film-forming resin, additive and solvent to 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 combinations 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 thereof etc.Importantly pearly pigment is being prepared into after the germicidal pearly coating of tool, and the color variation of coating is little, and has on the whole the even look of uniform light, and antibacterial function still has its effect.
Embodiment 8: the present embodiment is carried and supplied the germicidal pearly-lustre make-up composition of ー kind tool, and its production method comprises the following steps: (1) according to the experimental procedure of embodiment 4, and control TiO according to speed of reaction, reaction times and pH value
2how the height of rice rod, how rice rod is to form the pearly-lustre make-up composition of different colours to make the titanium dioxide of the coated different height of growing up of pearly pigment, and at TiO
2how on rice rod and flat substrates, metal refining silver makes its tool antibacterial effect, wherein titanium dioxide how a growth for rice rod highly can be 5～500 rice how, and the TiO of the different height of growing up
2how the colour-change of rice rod is as follows: being 5-80 how when rice as degree of growing tall, be blueness; How 80-100 when rice, be dark gold; How meter grow up is highly 110 time, is scarlet; Growing to 125 how when rice, is mazarine; Growing to 140 how when rice, is deep green; By that analogy, TiO afterwards
2how the excellent difference of rice is grown up highly, with every 15 how rice of meter Cheng Chang height Sustainable Growth to 500 how, the color of described pearly-lustre make-up composition can be with dark gold, scarlet, mazarine, bottle-green circular order, the variation that produces different interference color, obtain the germicidal pearly-lustre make-up composition of tool, can be applicable to the preparation of nail lustering agent, 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 at the growing state containing on the substratum of sample in table 1, sample YB219 utilizes preparation method of the present invention on commercially available pearly pigment, to adsorb the how result of rice rod of multiple titanium sesquioxides, sample YB219Ag be utilize be adsorbed on titanium sesquioxide on commercially available pearly pigment how a rice rod be oxidized to how rice rod of titanium dioxide, and argent carries out reduction reaction and be deposited on the how result on rice rod of titanium dioxide, its antibacterial detected result is:
(1) three of sample YB219 concentration all can suppress intestinal bacteria, to the equal unrestraint effect of staphylococcus aureus.
(2) three of sample YB219Ag concentration all can suppress intestinal bacteria and staphylococcus aureus.
Result demonstration, the deposition of high area argent on base material, makes to suppress the growth of intestinal bacteria and staphylococcus aureus.
Table 2 is for being made into the formula table of pearly coating, and sample 1 for adding the TiO with photocatalysis effect in coating
2how the coated pearly pigment of rice rod, sample 2 for adding the TiO with photocatalysis effect in coating
2coated pearly pigment, and at TiO
2depositing silver particle on surface.
Result demonstration, as shown in table 3, the photocatalysis effect of sample 1 (does not add TiO with respect to control group
2how rice rod), there is 85% Degradation Formaldehyde rate, and 80% carbon monoxide degradation rate, therefore can learn the present invention prepared there is high surface area TiO
2the coating how 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, owing to having multiple TiO on pearly pigment surface
2how rice rod and form high surface area and have the flat substrates of roughness, even if be prepared into coating, can not affect its TiO yet
2how the photocatalysis effect of rice rod; In addition, when further at TiO
2how rice rod is gone up after depositing silver particle, and as sample 2, the existence of silver particles has the effect of promoting photocatalytic activity, makes to have 93% Degradation Formaldehyde rate, and 90% carbon monoxide degradation rate, has further more promoted the peace and quiet power of environment.
Moreover sample 2 is because further increase the silver particles deposition of high surface area, even by coated silver TiO
2how the excellent pearly pigment of rice is prepared into coating, and sample 2 has antibacterial effect too and can suppress intestinal bacteria and staphylococcus aureus.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (5)
1. the germicidal pearly coating of tool, formed by a flat substrates and a film-forming resin, it is characterized in that, how rice is excellent on described flat substrates surface, to be covered with multiple spaced titanium dioxide, wherein said flat substrates has a full roughness Rz (DIN) between 5-500, and how described each titanium dioxide all deposit multiple silver particles on rice rod and described flat substrates.
2. the germicidal pearly coating of tool according to claim 1, described flat substrates is any base material in sheet mica, sheet glass, aluminium sesquioxide, flake aluminum, sheet pearlstone and silicon-dioxide.
3. the germicidal pearly coating of tool according to claim 2, the particle diameter of described flat substrates is 2-800 micron,, thickness is 0.1-10 micron.
4. the germicidal pearly coating of tool according to claim 1, described film-forming resin is any resin in epoxy resin, acrylic resin, urethane resin, polycarbonate resin, polyorganosiloxane resin, vinyl polymer resins, polyether resin, aminoplast(ic) resin and vibrin.
5. the germicidal pearly coating of tool according to claim 1, described flat substrates is a commercially available pearly pigment, described commercially available pearly pigment is take any in sheet mica, sheet glass, flake aluminum, sheet pearlstone, aluminium sesquioxide and silicon-dioxide as base material, wherein, the substrate surface of described any commercially available pearly pigment is coated with a kind of oxide compound in titanium dioxide, ferric oxide and silicon-dioxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104448949A (en) * | 2014-12-22 | 2015-03-25 | 常熟市环虹化工颜料厂 | Environment-friendly pearly luster composite pigment |
| CN104449269A (en) * | 2014-11-11 | 2015-03-25 | 黄勇 | Preparation method of antibacterial polyester paint |
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| JPH08199098A (en) * | 1995-01-20 | 1996-08-06 | Dainichiseika Color & Chem Mfg Co Ltd | Coating composition and formation of coating film |
| JP2007325995A (en) * | 2006-06-06 | 2007-12-20 | Univ Kinki | Photocatalyst film and its manufacturing method |
| CN101511948A (en) * | 2006-08-29 | 2009-08-19 | 日本板硝子株式会社 | Pearlescent pigment |
| CN102304313A (en) * | 2010-08-16 | 2012-01-04 | 江苏考普乐新材料股份有限公司 | Coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08199098A (en) * | 1995-01-20 | 1996-08-06 | Dainichiseika Color & Chem Mfg Co Ltd | Coating composition and formation of coating film |
| JP2007325995A (en) * | 2006-06-06 | 2007-12-20 | Univ Kinki | Photocatalyst film and its manufacturing method |
| CN101511948A (en) * | 2006-08-29 | 2009-08-19 | 日本板硝子株式会社 | Pearlescent pigment |
| CN102304313A (en) * | 2010-08-16 | 2012-01-04 | 江苏考普乐新材料股份有限公司 | Coating and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104449269A (en) * | 2014-11-11 | 2015-03-25 | 黄勇 | Preparation method of antibacterial polyester paint |
| CN104448949A (en) * | 2014-12-22 | 2015-03-25 | 常熟市环虹化工颜料厂 | Environment-friendly pearly luster composite pigment |
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