CN106633494A - Hard self-cleaning type plastic plate and preparation method thereof - Google Patents
Hard self-cleaning type plastic plate and preparation method thereof Download PDFInfo
- Publication number
- CN106633494A CN106633494A CN201611010155.9A CN201611010155A CN106633494A CN 106633494 A CN106633494 A CN 106633494A CN 201611010155 A CN201611010155 A CN 201611010155A CN 106633494 A CN106633494 A CN 106633494A
- Authority
- CN
- China
- Prior art keywords
- mentioned
- parts
- stirred
- added
- plastic plate
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a hard self-cleaning type plastic plate. The hard self-cleaning type plastic plate is prepared from the following raw materials in parts by weight: 3 to 4 parts of epoxidized soybean oil, 10 to 14 parts of titanium tetrachloride, 3.7 to 4 parts of ferric chloride, 6 to 8 parts of hydrogen peroxide of which the concentration is 25 to 30 percent, 7to 9 parts of methyl methacrylate, 0.1 to 0.2 part of azodiisobutyronitrile, 100 to 130 parts of polyvinyl chloride, 0.7 to 1 part of silane coupling agent kh 560, 2 to 3 parts of calcium stearate, 0.6 to 1 part of lauryl dimethyl amine oxide, 3 to 4 parts of polyethylene glycol, 1 to 2 parts of zinc stearate, 0.4 to 1 part of butyltin mercaptan, 1 to 2 parts of aluminum ammonium sulfate, 2 to 3 parts of palm wax, 0.7 to 1 part of polyimide and 4 to 5 parts of hydrated zinc borate. According to the hard self-cleaning type plastic plate disclosed by the invention, iron-doped titanium dioxide added in the hard self-cleaning type plastic plate has very good photocatalysis capacity and is capable of degrading and removing pollutants attached to the surface of the hard self-cleaning type plastic plate, so that self-cleaning performance is realized.
Description
Technical field
The present invention relates to board technology field, more particularly to a kind of hard self-clean type plastic plate and preparation method thereof.
Background technology
Titanium dioxide is a kind of transition metal oxide while being also a kind of semi-conducting material, because it has preferable life
The thing compatibility, can resist chemical attack, the advantages of harmless, meanwhile, the material abundance of titanium source content makes titanium dioxide thing
Produce abundant and cheap, therefore obtained people and widely pay close attention to, the application of titanium dioxide is embodied in each of people's life
Aspect, current titanium dioxide without mechanical goods usage amount has reached world lead level.Due to the characteristic of titanium dioxide, Ke Yizuo
For very important inorganic chemical industry material, therefore it has huge in various fields such as national defence aviation industry, commercial production, hard-core technologies
Big power of influence and application.Titanium dioxide can possess color as Chinese white using titanium white production coating out again
Bright-coloured, colorability is strong, and the advantages of covering power is high, and its service life is longer compared with other pigment, therefore its usage amount accounts for institute
Have the 80% of Chinese white.Rather than the other titanium dioxide of pigment-level still possesses the field of being widely applied, be concentrated mainly on metallurgy,
The fields such as ceramics, glass, sheet material；Because titanium dioxide has the ability and higher photocatalytic activity that absorb ultraviolet, therefore can
To prepare catalyst, adsorbent, antibacterial etc. using this characteristic, in the 70's of eighties of last century, people are found that to water
Middle addition titanium dioxide, under the irradiation of visible ray, water can resolve into oxygen and hydrogen.Subsequently, it is and special because of titanium dioxide
Some physicochemical properties and every excellent properties, so be widely used in numerous fields, including environment, the energy, information,
Material, health, building, medical treatment etc., especially in fields such as photocatalysis, solaode, gas sensor, sterilizations, embody very
Big researching value；
Nano titanium oxide has excellent photocatalytic activity, there is quite varied application prospect, however, there is also some
Weak point, nano titanium oxide just must can play a part of catalyst under the promotion of ultraviolet light, and solar energy is produced
Great waste, which greatly limits the use of nano titanium oxide.So we are needed by modified this
Method improves utilization of the nano titanium oxide to solar energy, allows it to make full use of the light of visible region.Research shows, when subtracting
During the size of little titanium dioxide nanoparticle, its surface area, surface tension can strengthen therewith with surface energy.Accordingly it is provided with little chi
The characteristics such as very little effect, quantum size effect, skin effect, it is widely used various that these speciality also cause titanium dioxide to become
Inorganic material product；
Catalysis material improves the living environment of people, and we can be not only used for using the photoelectric characteristic of catalysis material
Solaode is prepared, can be with degradation of contaminant, maintaining ecological balance.But the problem that needs are solved is, catalysis material
Solar energy more can't be efficiently utilized, this causes energy transition rate low or the shortcomings of poor photocatalytic degradation efficiency；On the one hand
Shortage of resources, is on the one hand unable to effectively utilizes effective energy（Visible light part）, will all cause the extreme loss of resource.Cause
This, for how improving titanium dioxide as the problem of photocatalysis efficiency, still needing to further research and improving；
Polyacrylate has pollution-free, low cost and other advantages, has obtained more wide in fields such as building, automobile, packaging, printings
General application, but there is also thermostability, hardness etc. it is poor the problems such as, limit to a certain extent its application, using inorganic nano
Titania modified polyacrylate, can significantly improve the performances such as hardness, thermostability, the impact strength of polyacrylate, from
And further expand its use range；
However, because the specific surface area of nano titanium oxide is big, surface energy is high, in non-thermodynamics stable state, prepared answers
The shortcomings of easily there is nanoparticle reunion, composite poor storage stability, complicated process of preparation in condensation material.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of hard self-clean type plastic plate and its system
Preparation Method.
The present invention is achieved by the following technical solutions：
A kind of hard self-clean type plastic plate, it is made up of the raw material of following weight parts：
Epoxy soybean oil 3-4, titanium tetrachloride 10-14, the hydrogen peroxide 6-8 of iron chloride 3.7-4,25-30%, methyl methacrylate
Ester 7-9, azodiisobutyronitrile 0.1-0.2, polrvinyl chloride 100-130, silane coupler kh5600.7-1, calcium stearate 2-3, the moon
Osmanthus base dimethyl amine 0.6-1, Polyethylene Glycol 3-4, zinc stearate 1-2, thiol-butyl tin 0.4-1, Burnt ammonium alum 1-2, palm fibre
Palmitic acid wax 2-3, polyimides 0.7-1, hydration zinc borate 4-5.
A kind of preparation method of described hard self-clean type plastic plate, comprises the following steps：
（1）Above-mentioned Burnt ammonium alum is added in the deionized water of its weight 20-23 times, is stirred, liter high-temperature is 64-70
DEG C, insulated and stirred 5-10 minute, above-mentioned palm wax is added, in being sent to 80-90 DEG C of water-bath, insulated and stirred 20-24 minute, go out
Material cooling, mixes with lauryl dimethyl amine oxide, 100-200 rev/min of stirring 6-10 minute, obtains aqueous dispersions；
（2）Above-mentioned titanium tetrachloride is added in the deionized water of its weight 60-70 times, is stirred, add above-mentioned iron chloride,
Deca concentration is the ammonia spirit of 5.4-6%, and regulation pH is 8-9, and sucking filtration will precipitate the deionization for being added to its weight 40-50 times
In water, ultrasonic 6-10 minutes, the hydrogen peroxide of above-mentioned 25-30% is added, magnetic agitation 20-30 minute, add above-mentioned moisture to dissipate
Liquid, the insulated and stirred 4-5 hour at 100-105 DEG C, in sending into 57-60 DEG C of baking oven, drying, discharging obtains Fe2O3 doping titanium dioxide
Titanium；
（3）Above-mentioned thiol-butyl tin is added in the dehydrated alcohol of its weight 6-8 times, is stirred, liter high-temperature is 76-80
DEG C, insulated and stirred 10-20 minute, in being sent to 90-95 DEG C of water-bath, add above-mentioned polyimides, zinc stearate, insulated and stirred
20-30 minutes, discharging obtains alcohol dispersion liquid；
（4）Above-mentioned silane coupler kh560 is taken, in being added to the acetone of its weight 50-60 times, Deca acetic acid, regulation pH is 5-
6, stir, above-mentioned Fe2O3 doping titanium dioxide is added, ultrasonic 20-30 minutes, sucking filtration obtains Silane Grafted titania-doped；
（5）Take above-mentioned Silane Grafted titania-doped, in being added to the dimethyl sulfoxide of its weight 37-40 times, ultrasonic 5-7 point
Clock, adds above-mentioned methyl methacrylate, azodiisobutyronitrile, and insulated and stirred 4-6 hour, centrifugation, obtain at 57-60 DEG C
Precipitation；
（6）Above-mentioned precipitation is added in alcohol dispersion liquid, is stirred, filtered, at 50-60 DEG C will be deposited in 1-2 is vacuum dried
Hour, obtain titania-doped graft polymers；
（7）Above-mentioned titania-doped graft polymers are mixed with remaining each raw material, insulated and stirred 1-2 is little at 70-80 DEG C
When, double screw extruder is sent into, extrusion, mould molding, cut off, overlay film, obtain final product the plastic plate.
It is an advantage of the invention that：Silane coupler is anchored in less aggregate surface by the present invention, reduces doping two
The surface energy and surface activity of Titanium particles, prevents doping particle itself that soft-agglomerated phenomenon occurs, due to the particle diameter that adulterates
Very little, enhance be covered in doping particle surface coupling agent molecule between active force and due to coupling agent adsorb and produce
Sterically hindered repulsive force, secondly, after polymethyl methacrylate is grafted on into silane treatment by original position emulsion graft polymerization
Particle surface, realizes organising completely for particle surface, and the carbochain for causing inorganic nano doping particle surface is extended, especially
After the linear long-chain molecule of polymethyl methacrylate is introduced by emulsion graft polymerization, hence it is evident that improve inorganic/organic biphase interface
Structure, increased the compatibility, improve the stability of composite；The titania-doped graft polymers meeting that the present invention is added
Increase the crosslink density between matrix resin molecule segment, cause organic matrix macromolecular chain certain distance from shortening, intermolecular work
Firmly strengthen, secondly, anchoring grafting and the realization of emulsion graft polymerization so that the two-phase interface compatibility is enhanced, bonding interface effect
Further it is reinforced, the final result of these effects results in organic molecule chain movement ability in system to be reduced, and is improve compound
The heat resistance of material, in addition, the Fe2O3 doping titanium dioxide that the present invention is added has good photo-catalysis capability, can be by sheet material
The contaminant degradation of surface attachment is removed, and so as to realize self-cleaning performance, the plate surface hardness of the present invention is high, and shock resistance is strong
Degree, crushing resistance are good, and combination property is superior.
Specific embodiment
A kind of hard self-clean type plastic plate, it is made up of the raw material of following weight parts：
Epoxy soybean oil 3, titanium tetrachloride 10, the hydrogen peroxide 6 of iron chloride 3.7,25%, methyl methacrylate 7, azo two are different
Butyronitrile 0.1, polrvinyl chloride 100, silane coupler kh5600.7, calcium stearate 2, lauryl dimethyl amine oxide 0.6, poly- second two
Alcohol 3, zinc stearate 1, thiol-butyl tin 0.4, Burnt ammonium alum 1, palm wax 2, polyimides 0.7, hydration zinc borate 4.
A kind of preparation method of described hard self-clean type plastic plate, comprises the following steps：
（1）Above-mentioned Burnt ammonium alum is added in the deionized water of 20 times of its weight, is stirred, it is 64 DEG C to rise high-temperature, is protected
Temperature stirring 5 minutes, adds above-mentioned palm wax, in being sent to 80 DEG C of water-bath, insulated and stirred 20 minutes, and discharging cooling, with Laurel
Base dimethyl amine mixes, and 100 revs/min are stirred 6 minutes, obtain aqueous dispersions；
（2）Above-mentioned titanium tetrachloride is added in the deionized water of 60 times of its weight, is stirred, add above-mentioned iron chloride, drop
Plus the ammonia spirit that concentration is 5.4%, it is 8 to adjust pH, and sucking filtration is added to precipitation in the deionized water of 40 times of its weight, ultrasound
6 minutes, above-mentioned 25% hydrogen peroxide, magnetic agitation 20 minutes is added to add above-mentioned aqueous dispersions, the insulated and stirred at 100 DEG C
4 hours, in sending into 57 DEG C of baking oven, drying, discharging obtained Fe2O3 doping titanium dioxide；
（3）Above-mentioned thiol-butyl tin is added in the dehydrated alcohol of 6 times of its weight, is stirred, it is 76 DEG C to rise high-temperature, is protected
Temperature stirring 10 minutes, in being sent to 90 DEG C of water-bath, adds above-mentioned polyimides, zinc stearate, insulated and stirred 20 minutes to go out
Material, obtains alcohol dispersion liquid；
（4）Above-mentioned silane coupler kh560 is taken, in being added to the acetone of 50 times of its weight, Deca acetic acid, it is 5 to adjust pH, stirring
Uniformly, above-mentioned Fe2O3 doping titanium dioxide is added, ultrasonic 20 minutes, sucking filtration obtains Silane Grafted titania-doped；
（5）Take that above-mentioned Silane Grafted is titania-doped, in being added to the dimethyl sulfoxide of 37 times of its weight, ultrasound 5 minutes, plus
Enter above-mentioned methyl methacrylate, azodiisobutyronitrile, insulated and stirred 4 hours at 57 DEG C, centrifugation must be precipitated；
（6）Above-mentioned precipitation is added in alcohol dispersion liquid, is stirred, filtered, be vacuum dried 1 hour at 50 DEG C will be deposited in,
Obtain titania-doped graft polymers；
（7）Above-mentioned titania-doped graft polymers are mixed with remaining each raw material, insulated and stirred 1 hour, send at 70 DEG C
Enter double screw extruder, extrusion, mould molding, cut off, overlay film, obtain final product the plastic plate.
Performance test：
Tensile strength： 48.3MPa；
Bending strength： 71MPa；
Anti-flammability：Put out from fire, without black smoke.
Claims (2)
1. a kind of hard self-clean type plastic plate, it is characterised in that it is made up of the raw material of following weight parts：
Epoxy soybean oil 3-4, titanium tetrachloride 10-14, the hydrogen peroxide 6-8 of iron chloride 3.7-4,25-30%, methyl methacrylate
Ester 7-9, azodiisobutyronitrile 0.1-0.2, polrvinyl chloride 100-130, silane coupler kh5600.7-1, calcium stearate 2-3, the moon
Osmanthus base dimethyl amine 0.6-1, Polyethylene Glycol 3-4, zinc stearate 1-2, thiol-butyl tin 0.4-1, Burnt ammonium alum 1-2, palm fibre
Palmitic acid wax 2-3, polyimides 0.7-1, hydration zinc borate 4-5.
2. a kind of preparation method of hard self-clean type plastic plate as claimed in claim 1, it is characterised in that including following step
Suddenly：
（1）Above-mentioned Burnt ammonium alum is added in the deionized water of its weight 20-23 times, is stirred, liter high-temperature is 64-70
DEG C, insulated and stirred 5-10 minute, above-mentioned palm wax is added, in being sent to 80-90 DEG C of water-bath, insulated and stirred 20-24 minute, go out
Material cooling, mixes with lauryl dimethyl amine oxide, 100-200 rev/min of stirring 6-10 minute, obtains aqueous dispersions；
（2）Above-mentioned titanium tetrachloride is added in the deionized water of its weight 60-70 times, is stirred, add above-mentioned iron chloride,
Deca concentration is the ammonia spirit of 5.4-6%, and regulation pH is 8-9, and sucking filtration will precipitate the deionization for being added to its weight 40-50 times
In water, ultrasonic 6-10 minutes, the hydrogen peroxide of above-mentioned 25-30% is added, magnetic agitation 20-30 minute, add above-mentioned moisture to dissipate
Liquid, the insulated and stirred 4-5 hour at 100-105 DEG C, in sending into 57-60 DEG C of baking oven, drying, discharging obtains Fe2O3 doping titanium dioxide
Titanium；
（3）Above-mentioned thiol-butyl tin is added in the dehydrated alcohol of its weight 6-8 times, is stirred, liter high-temperature is 76-80
DEG C, insulated and stirred 10-20 minute, in being sent to 90-95 DEG C of water-bath, add above-mentioned polyimides, zinc stearate, insulated and stirred
20-30 minutes, discharging obtains alcohol dispersion liquid；
（4）Above-mentioned silane coupler kh560 is taken, in being added to the acetone of its weight 50-60 times, Deca acetic acid, regulation pH is 5-
6, stir, above-mentioned Fe2O3 doping titanium dioxide is added, ultrasonic 20-30 minutes, sucking filtration obtains Silane Grafted titania-doped；
（5）Take above-mentioned Silane Grafted titania-doped, in being added to the dimethyl sulfoxide of its weight 37-40 times, ultrasonic 5-7 point
Clock, adds above-mentioned methyl methacrylate, azodiisobutyronitrile, and insulated and stirred 4-6 hour, centrifugation, obtain at 57-60 DEG C
Precipitation；
（6）Above-mentioned precipitation is added in alcohol dispersion liquid, is stirred, filtered, at 50-60 DEG C will be deposited in 1-2 is vacuum dried
Hour, obtain titania-doped graft polymers；
（7）Above-mentioned titania-doped graft polymers are mixed with remaining each raw material, insulated and stirred 1-2 is little at 70-80 DEG C
When, double screw extruder is sent into, extrusion, mould molding, cut off, overlay film, obtain final product the plastic plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611010155.9A CN106633494A (en) | 2016-11-17 | 2016-11-17 | Hard self-cleaning type plastic plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611010155.9A CN106633494A (en) | 2016-11-17 | 2016-11-17 | Hard self-cleaning type plastic plate and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106633494A true CN106633494A (en) | 2017-05-10 |
Family
ID=58808288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611010155.9A Pending CN106633494A (en) | 2016-11-17 | 2016-11-17 | Hard self-cleaning type plastic plate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106633494A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587047A (en) * | 2018-03-22 | 2018-09-28 | 长沙小新新能源科技有限公司 | A kind of fluorinated plastic and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602147A (en) * | 2016-01-29 | 2016-05-25 | 宁波远欣石化有限公司 | Anticorrosion stable anti-aging plastic plate |
-
2016
- 2016-11-17 CN CN201611010155.9A patent/CN106633494A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602147A (en) * | 2016-01-29 | 2016-05-25 | 宁波远欣石化有限公司 | Anticorrosion stable anti-aging plastic plate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587047A (en) * | 2018-03-22 | 2018-09-28 | 长沙小新新能源科技有限公司 | A kind of fluorinated plastic and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101613537B (en) | Method for preparing nano silicon dioxide coated by nano titanium dioxide | |
| CN105646944B (en) | A kind of preparation method of organically-modified molybdenum disulfide nano sheet | |
| CN108440696A (en) | A kind of polyalcohol hydrogel and its preparation and application based on two-dimentional titanium carbide layer shape compound crosslink | |
| CN101514263A (en) | Modified white carbon black and preparation method thereof | |
| CN106397838A (en) | Modified calcium carbonate for cables | |
| CN104559935A (en) | Composite-wall phase-change energy storing microcapsule and preparation method thereof | |
| CN110564096A (en) | Anti-ultraviolet nano lignin composite membrane and preparation method thereof | |
| CN110256759B (en) | Environment-friendly wear-resistant anti-slip foam composite material for shoes and preparation method thereof | |
| CN111875814A (en) | Preparation method of modified rubber powder by sol-gel method | |
| CN106633494A (en) | Hard self-cleaning type plastic plate and preparation method thereof | |
| CN106496873A (en) | A kind of hydrophobic impervious self-clean type plastic plate and preparation method thereof | |
| CN107513118A (en) | A kind of preparation method of titanium dioxide/polyacrylamide nano composite | |
| CN106589662A (en) | Microcellular foaming self-cleaning type plastic plate and preparation method thereof | |
| CN106496870A (en) | A kind of fluorination self-clean type plastic plate and preparation method thereof | |
| CN106633496A (en) | Anti-impact self-cleaning plastic plate and preparation method thereof | |
| CN106589668A (en) | Titanium dioxide-doped self-cleaning plastic plate and preparation method thereof | |
| CN106496872A (en) | A kind of antioxidation self-clean type plastic plate and preparation method thereof | |
| CN106496871A (en) | A kind of fiber reinforced self-clean type plastic plate and preparation method thereof | |
| CN106751121A (en) | A kind of lightweight self-clean type plastic plate and preparation method thereof | |
| CN106750781A (en) | Using the plastic pellet of SBS modified waste high density polyethylene (HDPE)s | |
| CN106633299B (en) | A kind of polyethylene/montmorillonite carried titanium dioxide composite material and preparation method | |
| CN106589663A (en) | Self-cleaned plastic sheet material and preparation method therefor | |
| CN106589665A (en) | Bacteriostatic and self-cleaned plastic sheet material and preparation method therefor | |
| CN106496869A (en) | A kind of fire-retardant self-clean type plastic plate and preparation method thereof | |
| CN103897577A (en) | Glass paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170510 |
|
| WD01 | Invention patent application deemed withdrawn after publication |