CN109928655A - Hud typed anticoagulant ice modifying agent, its manufacturing method and the anticoagulant ice coating including it - Google Patents
Hud typed anticoagulant ice modifying agent, its manufacturing method and the anticoagulant ice coating including it Download PDFInfo
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- CN109928655A CN109928655A CN201910262407.4A CN201910262407A CN109928655A CN 109928655 A CN109928655 A CN 109928655A CN 201910262407 A CN201910262407 A CN 201910262407A CN 109928655 A CN109928655 A CN 109928655A
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Abstract
The present invention relates to a kind of hud typed anticoagulant ice modifying agent, its manufacturing method and including its anticoagulant ice coating.Hud typed anticoagulant ice modifying agent of the invention includes core and shell, and the core is water-soluble metal salt particle, and the shell is formed by oxide particle and the shell cladding core, wherein the shell with a thickness of 10nm or more.Hud typed anticoagulant ice modifying agent of the invention is easy construction, and when being used for anticoagulant ice coating, has excellent anticoagulant ice, hydrophobicity, slow release and lasting service life by the anticoagulant ice coating that such anticoagulant ice coating is formed.
Description
Technical field
The present invention relates to a kind of hud typed anticoagulant ice modifying agent, its manufacturing method and including its anticoagulant ice coating.
Background technique
It is always the problem of perplexing highway traffic safety that winter road snow, which freezes,.It is anti-that road snow icing will lead to road surface
Sliding ability is greatly lowered, and has both weakened the traffic capacity of road, has been easy to produce pernicious traffic accident, but can destroy road and its
Attached structure will cause interruption of communication, be normally carried out people's lives and production can not, or even endangers the people's life when serious
The safety of life and property.
Currently, common road surface deicing snow method is generally divided into passive suppressive and active ice-melt snow type two major classes.It is logical
Frequently with passive suppressive deicing measure mainly include dispensing the measures such as deicing salt, artificial snow removing, snow removal with machine.Usually spread
The main component of the metal chloride deicing salt of cloth is sodium chloride, calcium chloride, magnesium chloride, potassium chloride etc., is guaranteeing that traffic is smooth
While logical, traffic safety, corrosion and welding also are caused to infrastructure.Artificial snow removing and snow removal with machine low efficiency, consumption
Duration, especially snow removal with machine need to purchase the snow removing equipment of profession, road pavement is had damage.Active ice-melt snow type technology mainly passes through
The specific function on road surface realizes deicing snow melt, including seif-citing rate elasticity road-surface-paving technology, energy transformant ice-melt avenge technology
Deng.Active ice-melt snow type technology is still immature, and practical operation has difficulties.
After prolonged scientific research and application, cost, maintenance, action time and the case where using effect are being considered
Under, it is believed that by coating bituminous pavement using anticoagulant ice coating to obtain the technology of anticoagulant ice coating on road surface as relatively rationally
Technology.
Anticoagulant ice coating is that a new generation as obtained from organic hydrophobic materials and the compounding of anticoagulant ice modifying agent is functional
Road paint.The technology overcomes previous maintenance technology to be difficult to the drawbacks of constructing under low temperature environment in winter.Organic hydrophobic materials
There is excellent adhesiveness with road surface, and there is ventilative water shutoff and self-cleaning performance, so as to remove surface covering automatically
Dust restores anticoagulant ice modifying agent to the inhibiting effect of freezing point, actively maintains deicing function.Resist included in anticoagulant ice coating
Solidifying ice modifying agent cardinal principle is in the case where capillary pressure and vehicle roll effect, and the ingredient of internal inhibition freezing efficiency is gradually
It is precipitated, to reduce the freezing point of road surface water, road surface accumulated snow is inhibited to freeze.Therefore, it is protected for use cost and environment
The needs of shield, it is desirable that anticoagulant ice modifying agent used in anticoagulant ice coating has excellent slow release.In the prior art for
Some researchs have been carried out in anticoagulant ice coating and anticoagulant ice modifying agent.
A kind of three component road surface deicing snow melt coating of slow-release is disclosed in patent document 1, wherein used resin is
Organosilicon material and use include being carried on the suppression ice component of salt and carbon black on such as zeolite porous adsorption carrier.However,
Although the coating has slow release and anticoagulant ice, complicated composition and preparation process is cumbersome cause to be unfavorable for for road
The site operation in face；In addition, the anticoagulant ice and slow release of suppression ice component still need to be further increased.
Disclosing in patent document 2 a kind of has slow-release function super-hydrophobic ice-covering-proof coating comprising fluoropolymer and
By the inorganic hollow or porous nano particle of the anti-icing substance of absorption small molecule.The coating has excellent hydrophobicity and slow release,
But fluoropolymer-containing higher cost and by the anti-of the inorganic hollow of the anti-icing substance of absorption small molecule or porous nano particle
Solidifying ice and slow release are insufficient.
A kind of organic coating slow-release long-acting environment friendly snow melt ice melting agent is disclosed in patent document 3, can be used for from snow melt
In coating, preparation method heats including the use of double screw extruder and is compounded snow melt salt and organic coating agent.Although the snow melt
Ice melting agent can reduce freezing point, but do not paid close attention in patent document 3 the snow melt ice melting agent when for anticoagulant ice coating whether
It is able to maintain its performance.In addition, patent document 3 using double screw extruder and exist heating and cooling process, production cost compared with
It is high.
In addition, also taking coated inorganic salt using wax, pitch etc. in the prior art to assign slow release.However, the present inventor
Find after study, anticoagulant ice modifying agent be used for anticoagulant ice coating when because be formed by anticoagulant ice coating layer thickness 1mm with
Under, anticoagulant ice modifying agent is needed using in powdered inorganic salt particle (particle size is about at 5-20 microns).Thus, it is existing
Technology has the following problems: since inorganic salt particle is smaller (large specific surface area), used wax, pitch or various resins
The dosage of (such as patent document 3) can be very big, uneconomical；It is wrapped up using this simple physics mode, particle surface package is difficult to
Uniformly, and organic matter has viscosity, and the particle after package can bond together, subsequent in order to make the particle of bonding scatter
Production work amount can be very huge, it is difficult to realize really industrialization；Further, it finds in actual use, using using
In the short grained situation of polymer wrapped inorganic salts, the void ratio of lapping is more on the inorganic salt particle surface after package,
Slow release effect can be made to substantially reduce after meeting water.
Existing technical literature
Patent document 1:CN103805059A
Patent document 2:CN102382536A
Patent document 3:CN107699199A
Summary of the invention
Problems to be solved by the invention
In view of the above problems, the purpose of the present invention is to provide a kind of hud typed anticoagulant ice modifying agent, are easy construction, and
And when being used for anticoagulant ice coating, there is excellent anticoagulant ice by the anticoagulant ice coating that such anticoagulant ice coating is formed, dredge
Aqueous, slow release and lasting service life.
It is a further object of the present invention to provide the manufacturing methods of aforementioned anticoagulant ice agent, can come in a straightforward manner real
It applies.
It is yet another object of the invention to provide the anticoagulant ice coating comprising aforementioned anticoagulant ice agent, by such anticoagulant ice coating
The anticoagulant ice coating formed can have excellent anticoagulant ice, hydrophobicity, slow release and lasting service life.
The solution to the problem
The present invention has been made in the further investigation of inventor through the invention, specific as follows.
[1] a kind of hud typed anticoagulant ice modifying agent comprising core and shell, the core are water-soluble metal salt
Grain, the shell is formed by oxide particle and the shell coats the core；The shell with a thickness of 10nm or more.
[2] the hud typed anticoagulant ice modifying agent according to [1], the oxide particle are silica dioxide granule or dioxy
Change titanium particle.
[3] the hud typed anticoagulant ice modifying agent according to [1] or [2], the water-soluble metal salt be selected from sodium chloride,
At least one of calcium chloride, magnesium chloride, calcium acetate, magnesium acetate, potassium acetate.
[4] manufacturing method of the described in any item hud typed anticoagulant ice modifying agent in a kind of basis [1]-[3], comprising:
It is dispersed in water-soluble metal salt in the alcohols solvent as initial dispersion medium, then adds alkali thereto
Property catalyst, is optionally added deionized water, obtains pre-dispersed liquid；
Under stiring, it in Xiang Suoshu pre-dispersed liquid, adds the presoma of oxide particle and is reacted；
Solid component is obtained by filtration, and is washed and is dried.
[5] manufacturing method according to [4], the basic catalyst are selected from ammonium hydroxide, sodium hydroxide, potassium hydroxide
It is at least one.
[6] a kind of anticoagulant ice coating, comprising: relative to the organic silicon-type material of 100 mass parts, the drip of 10-70 mass parts
Blueness, the curing catalysts of 0.5-5.0 mass parts, 10-55 mass parts the described in any item hud typed anticoagulant ice in basis [1]-[3]
Modifying agent.
[7] the anticoagulant ice coating according to [6], the organic silicon-type material are to change selected from organic siliconresin, organosilicon
Property polyurethane resin, modifying epoxy resin by organosilicon, organosilicon-modified acrylate system resin, fluorine richness organic siliconresin,
Silicone modified polyester resin, Effect of Organosilicon-modified Phenol-formaldehyde Resin, organosilicon-modified styrene-acrylic rubber, organic-silicon-modified butadiene-styrene rubber
It is at least one.
[8] the anticoagulant ice coating according to [6] or [7], further includes filler.
[9] the anticoagulant ice coating according to [8], further includes silane coupling agent.
The effect of invention
Hud typed anticoagulant ice modifying agent of the invention is easy construction.The hud typed anticoagulant ice modifying agent is to ambient enviroment friend
Good, when being used for anticoagulant ice coating, the anticoagulant ice coating that is formed by such anticoagulant ice coating can be in 0~-30 DEG C of low temperature
Under also have excellent anticoagulant ice；The hud typed anticoagulant ice modifying agent has the shell formed by oxide particle, thus has
There is excellent hydrophobicity, can also substantially slow down the speed for releasing water-soluble metal salt, that is, there is excellent slow release.
Raw material sources in the manufacturing method of the present invention are extensive, cheap, while it is not necessary that coupling is added in technical process
The auxiliary agents such as agent, surfactant, reaction condition is mild, and experimental period is short.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) picture of industrial NaCl used in Production Example.
Fig. 2 is NaCl/SiO in Production Example 12Scanning electron microscope (SEM) picture of Core-shell Composite Particles.
Fig. 3 is NaCl/SiO in Production Example 22Scanning electron microscope (SEM) picture of Core-shell Composite Particles.
Fig. 4 is shown when water droplet drips to uncoated glass slide and with being formed by the anticoagulant ice coating of embodiment 1 respectively
Water droplet state when on the glass slide of coating.
Fig. 5 is shown when water droplet drips to uncoated prevailing roadway and with being formed by the anticoagulant ice coating of embodiment 1 respectively
Coating road surface on situation.
The deicing that Fig. 6 shows the coating formed by reference coating and the coating formed by the anticoagulant ice coating of embodiment 1 is imitated
Fruit.
Specific embodiment
<<hud typed anticoagulant ice modifying agent>>
It includes core and shell to hud typed anticoagulant ice modifying agent of the invention, and the core is water-soluble metal salt
Grain, the shell is formed by oxide particle and the shell coats the core.The shell with a thickness of 10nm or more.
The core and shell for constituting hud typed anticoagulant ice modifying agent of the invention will will be described in detail below.
<core>
The core of hud typed anticoagulant ice modifying agent of the invention is water-soluble metal salt particle.Water-soluble metal salt particle is
The effective component of hud typed anticoagulant ice modifying agent of the invention is excellent to provide for adjusting the freezing point of the water on road surface
Anticoagulant ice.
The type of water-soluble metal salt particle of the invention is not particularly limited, can be in this field for adjusting
Any known metal salt of the freezing point of water on road surface.From the viewpoint of being preferably provided anticoagulant ice and is easier to obtain, this
The type of the water-soluble metal salt particle of invention is the acetic acid of chloride selected from alkali metal, alkali formate, alkali metal
Salt, the chloride of alkaline-earth metal, the formates of alkaline-earth metal, alkaline-earth metal acetate at least one.It is highly preferred that this hair
Bright water-soluble metal salt be preferably selected from sodium chloride, calcium chloride, magnesium chloride, calcium acetate, magnesium acetate, potassium acetate at least one
Kind.
There is no limit can be according to this hair for the ratio of the various metal salts of the water-soluble metal salt particle of the invention to composition
The use temperature of bright hud typed anticoagulant ice modifying agent properly selects.For example, in the use of hud typed anticoagulant ice modifying agent
When temperature is 0 to -10 DEG C, the mass ratio of sodium chloride and calcium chloride (magnesium chloride) can be 50-90:50-10, preferably 55-85:
45-15, more preferably 60-80:40-20；And when the use temperature of hud typed anticoagulant ice modifying agent is lower than -10 DEG C, chlorination
The mass ratio of sodium and calcium chloride (magnesium chloride) is 10-40:90-60, preferably 15-35:85-55, more preferably 20-30:80-
70。
The shape of water-soluble metal salt particle of the invention is not particularly limited, water-soluble metal salt particle of the invention
For the commercially available other metal salt of technical grade.In order to preferably can be used in anticoagulant ice coating, water-soluble metal of the invention
Grain is preferably dimensioned to be 5-20 μm.
<shell>
The shell of anticoagulant ice modifying agent of the invention is formed by oxide particle, and the shell coats above-mentioned core.
In the present invention, shell is used to encapsulate the water-soluble metal salt particle as core and has the stronger binding force with core,
Anticoagulant ice coating can be assigned when thus in for anticoagulant ice coating with excellent slow release and there is excellent and resin
Compatibility and stability.
Further, the shell in the present invention with a thickness of 10nm or more, in general, the upper thickness limit to shell does not limit,
It can suitably be selected according to the type and practical use of oxide particle.Further, from the viewpoint of slow release and cost, this hair
The thickness of shell in bright is more preferably 10nm-200nm, and more preferably 15nm-160nm, still more preferably 20-130nm.When
When the thickness of shell is less than above range, the slow release of anticoagulant ice modifying agent of the invention tends to deteriorate.When the thickness of shell is big
When above range, it will not further improve slow release and cost can be improved.
In the present invention, it is not particularly limited for constituting the type of oxide particle of shell, as long as it can be by molten
Glue-gel method coats core.For example, the example of such oxide particle includes silicon, aluminium, phosphorus, boron and transition metal element
Oxide particle.They can be used alone or are applied in combination with two or more.Preferably, oxide particle is titanium dioxide
Silicon particle or titanium dioxide granule, at low cost because of the application of both oxides and from a wealth of sources, chemical property and physical
It can stablize.For example, silica is nontoxic and has good biocompatibility, titanium dioxide has excellent photocatalysis
Property.
In addition, constituting shell of the invention from being more easily formed shell and obtaining the viewpoint of superior slow release
The partial size of oxide particle is preferably 2-100nm, more preferably 5-80nm.
Further, it can also be doped into other element simple substances and change as needed in anticoagulant ice modifying agent shell of the invention
Object is closed, to assign other functions, such as uviolresistance, antistatic property, anti-flammability etc. to shell.In addition, of the invention is anti-
The surface (i.e. the outer surface to environment in shell face) of solidifying ice modifying agent can also carry out various physics and chemical modification as needed
Processing, thus the performance of anticoagulant ice Modifiers Surface according to actual needs.
<<manufacturing method of hud typed anticoagulant ice modifying agent>>
The manufacturing method of hud typed anticoagulant ice modifying agent of the invention is actually the manufacturer based on sol-gel method
Method.The chemical process of sol-gel method is that raw material passes through hydrolysis in a solvent to generate activated monomer, activated monomer into
Row polymerization starts to become colloidal sol, and then generates the gel with certain space structure, needed for preparing by dry and heat treatment
Want material.It is modified currently, rarely having carry out cladding as anticoagulant ice to water-soluble metal salt using sol-gel method in the prior art
The technology of agent.
Specifically, the manufacturing method of the present invention includes: to be dispersed in water-soluble metal salt in alcohols solvent, then
Thereto, basic catalyst is added, deionized water is optionally added, obtains pre-dispersed liquid (preparation step of pre-dispersed liquid)；It is stirring
It mixes down, in Xiang Suoshu pre-dispersed liquid, adds the presoma of oxide particle and reacted (sol-gel forming step)；It crosses
Filter obtains solid component, and is washed and dried (shell forming step).
Each step will will be described in detail below.
<preparation step of pre-dispersed liquid>
In the preparation step of pre-dispersed liquid, it is dispersed in water-soluble metal salt in alcohols solvent, then thereto,
Basic catalyst is added, deionized water is optionally added, obtains pre-dispersed liquid.
As initial dispersion medium, the specific example of alcohols solvent used in pre-dispersed liquid includes methanol, ethyl alcohol, just
Propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, neopentyl alcohol, n-hexyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, benzene
Ethyl alcohol, ethylene glycol.They can be used alone or are applied in combination with two or more.From further improving productive viewpoint,
Alcohols solvent of the invention is preferably one of methanol, ethyl alcohol, isopropanol or a variety of, more preferably ethyl alcohol.
The details of water-soluble metal salt particle describe above, and details are not described herein again.From being more easily formed shell
Layer and further improve productive viewpoint, in this step in resulting pre-dispersed liquid, relative to as initial dispersion medium
Alcohols solvent total amount, the concentration for dispersing water-soluble metal salt is preferably 5-50g/ml, preferably 10-45g/ml, more preferably
For 12-35g/ml.
In the present invention, used sol gel catalyst is not particularly limited, as long as it can cause colloidal sol-solidifying
Glue process.The specific example of sol gel catalyst includes such as ammonium hydroxide, sodium hydroxide, potassium hydroxide alkali compounds
With the acid compounds such as such as hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, acetic acid, phthalic acid.
From the viewpoint for being more easily formed shell, sol gel catalyst of the invention is alkali compounds.In this step
The pH for being formed by pre-dispersed liquid is preferably 7.5-11.5, more preferably 8.0-10.0.
In certain preferred embodiments of the invention, from the viewpoint for the formation that can more easily control shell, preferably
The ammonium hydroxide for the use of concentration being 25-28%.In the case, the total amount relative to the alcohols solvent as initial dispersion medium, ammonia
The dosage of water is preferably 0.5-10 volume %, more preferably 0.8-6 volume %, more preferably 1-3 volume %.When the dosage of ammonium hydroxide
When less than above range, oxide particle forms speed and tended to be slow.When the dosage of ammonium hydroxide is greater than above range, it is free on anti-
The quantity of the oxide particle in system is answered to tend to excessively, oxide particle be caused to tend to be difficult to be coated on water-soluble metal salt
On.
Further, pre-dispersed liquid of the invention optionally includes deionized water.From be more easily formed shell and make gained
Anticoagulant ice modifying agent there is the viewpoint of better slow release, pre-dispersed liquid of the invention preferably comprises deionized water.In this feelings
Under condition, relative to the total amount of the alcohols solvent as initial dispersion medium, the dosage of deionized water of the invention is preferably 2-20
Volume %, and more preferably 3-16 volume %.When the dosage of deionized water is less than above range, before following oxide particles
The hydrolysis for driving body tends to be insufficient.When the dosage of deionized water is greater than above range, the oxide that is free in reaction system
The quantity of particle tends to excessively, oxide particle be caused to tend to be difficult to be coated on water-soluble metal salt.
In this step, the addition form of deionized water is not particularly limited, can individually be added, can also with alcohol
The form of the mixture of class solvent is added.Preferably, deionized water is added in the form of the mixture with alcohols solvent, in this feelings
Under condition, the volume ratio (deionized water/alcohols solvent) of deionized water and alcohols solvent is preferably 0.2/10 to 12/10, more preferably
0.8/10 to 10/10, and more preferable 1/10 to 6/10.The example of the alcohols solvent mixed with deionized water with about above-mentioned conduct
It is identical listed by the alcohols solvent of initial dispersion medium.In the present invention, it is highly preferred that the alcohols mixed with deionized water is molten
Agent is identical as the above-mentioned alcohols solvent as initial dispersion medium.
<sol-gel forming step>
In sol-gel forming step, under stiring, in the pre-dispersed liquid obtained in preceding step, addition oxidation
The presoma of composition granule is simultaneously reacted.
The presoma of oxide particle is not particularly limited.Theoretically, can be used can be by sol-gal process shape
At whole presomas of oxide.The specific example of the presoma of oxide particle includes silicon, aluminium, phosphorus, boron and transition metal member
Inorganic salts (including halide) or alkoxide compound of element etc..Further, from the viewpoint of productivity and cost, can preferably make
With silicon or the alkoxide compound of titanium；Quanmethyl silicate, tetraethyl orthosilicate, silicic acid orthocarbonate, silicic acid are selected from even more preferably from using
Four butyl esters at least one or selected from tetramethoxy titanate ester, tetraethyl titanate, metatitanic acid orthocarbonate, butyl titanate at least one
Kind.
In general, do not limit the dosage of the presoma of oxide particle, if resulting shell with a thickness of 10nm with
It is upper.The dosage of the presoma of oxide particle can suitably be selected according to the type of presoma.In general, working as oxide particle
When being formed by silica, the mass ratio of silica precursor and water-soluble metal salt is preferably 0.1/1-2/1, more preferably
0.15/1-1.5/1, and more preferable 0.2/1-1/1；And when oxide particle is formed by titanium dioxide, TiO 2 precursor
Mass ratio with water-soluble metal salt is preferably 0.08/1-1.2/1, more preferable 0.1/1-1/1, and more preferable 0.15/1-0.8/
1。
In this step, the presoma of oxide particle can be added individually, can also be with the mixture with alcohols solvent
Form addition.Preferably, the presoma of oxide particle is added in the form of the mixture with alcohols solvent, in this situation
Under, the presoma of oxide particle and the volume ratio of alcohols solvent are preferably 0.2/10 to 12/10, more preferable 0.8/10 to 10/
10, and more preferable 1/10 to 6/10.The example of the alcohols solvent mixed with the presoma of oxide particle with about above-mentioned conduct
It is identical listed by the alcohols solvent of initial dispersion medium.In the present invention, it is highly preferred that the presoma with oxide particle is mixed
The alcohols solvent of conjunction is identical as the above-mentioned alcohols solvent as initial dispersion medium.
The addition manner of the presoma of oxide particle is not particularly limited, can be added, can also be added in batches with a step
Enter.Preferably, in the present invention, the presoma of oxide particle is added to a step.
In the present invention, after the presoma of addition oxide particle, hydrolysis-condensation reaction occurs, to be formed solidifying
Glue.Reaction temperature is preferably 20-60 DEG C, from the viewpoint of handling ease, more preferably room temperature.Reaction time according to reaction temperature and
Variation, preferably 6-24h, more preferably 8-16h.
<shell forming step>
In shell forming step, after the completion of aforementioned hydrolysis-condensation reaction, solid component is obtained by filtration, and carry out
Washing and drying.
Filter device employed in this step is not particularly limited, can be used conventionally known for being separated by solid-liquid separation
Device.
It is washed via the solid component being obtained by filtration, to remove unreacted raw material, uncoated oxide
Particle and sol gel catalyst ingredient.It is preferable to use identical as the above-mentioned alcohols solvent as initial dispersion medium for washing
Solvent.
Dry temperature is not particularly limited, but usually 20-98 DEG C, preferably 20-60 DEG C, from productive sight
Point, more preferably room temperature.
<other steps>
Other than above step, as needed, the manufacturing method of anticoagulant ice modifying agent of the invention can also include to institute
The anticoagulant ice modifying agent obtained is classified, is measured, is packed.
<<application of hud typed anticoagulant ice modifying agent>>
Hud typed anticoagulant ice modifying agent of the invention can be used for various bituminous pavements in anticoagulant ice coating, to assign institute
The anticoagulant ice coating formed is with hydrophobicity and anticoagulant ice.Most preferably, when hud typed anticoagulant ice modifying agent of the invention is used for
When in anticoagulant ice coating of the invention, the anticoagulant ice coating that thus anticoagulant ice coating is formed can have excellent anticoagulant ice,
Hydrophobicity, slow release and lasting service life.
<<anticoagulant ice coating>>
Anticoagulant ice coating of the invention can form anticoagulant ice coating on being coated on bituminous pavement and after solidification.
Specifically, anticoagulant ice coating of the invention includes the organic silicon-type material relative to 100 mass parts, 10-70 matter
Measure the pitch of part, the curing catalysts of 0.5-5.0 mass parts, 10-55 mass parts hud typed anticoagulant ice modifying agent of the invention.
It should be noted that the amount of " the organic silicon-type material relative to 100 mass parts " used herein refer to each component solid at
Content of the split-phase for organic silicon-type material solid ingredient.
In the anticoagulant ice coating of the invention, physics and chemistry between anticoagulant ice modifying agent of the invention and other compositions
Act on (compatibility) well, therefore anticoagulant ice modifying agent is not easy to be destroyed in use, can keep for a long time its anticoagulant ice and
Slow release；In addition, existing at a specific ratio between organic silicon-type material and pitch, so that the resulting coating after paint solidification
Excellent hydrophobicity, strong binding force, the impact of resistance to external force with road surface are shown, so as to improve the service life of coating.
Hud typed anticoagulant ice modifying agent of the invention is described in detail above, therefore details are not described herein again.It needs to infuse
Meaning, relative to the organic silicon-type material of 100 mass parts, the content of hud typed anticoagulant ice modifying agent of the invention is preferably
15-45 mass parts, more preferably 20-40 mass parts.When the content of hud typed anticoagulant ice modifying agent is greater than above range, make
The amount of the anticoagulant ice ingredient (water-soluble metal salt) discharged with period tends to be excessive, leads to the negative effect to environment.Work as core
When the content of the anticoagulant ice modifying agent of shell mould is less than above range, anticoagulant ice tends to deteriorate.
To will be described in detail below constitute in anticoagulant ice coating of the invention in addition to above-mentioned hud typed anticoagulant ice modifying agent with
Outer other compositions.
<organic silicon-type material>
In the present invention, when organic silicon-type material is used for anticoagulant ice coating, the anticoagulant ice formed after solidifying can be made to apply
There is strong binding force between layer and bituminous pavement, and at the same time provide good hydrophobicity and with it is of the invention hud typed anticoagulant
The compatibility of ice modifying agent, to improve service life and anticoagulant ice.
Organic silicon-type material of the invention is the polymer of the repetitive unit with silicon oxygen bond (- Si-O-) in the molecule, can
To crosslink solidification in the presence of curing catalysts.Preferably, organic silicon-type material is selected from organic siliconresin, organosilicon
The organosilicon tree of modified polyurethane resin, modifying epoxy resin by organosilicon, organosilicon-modified acrylate system resin, fluorine richness
Rouge, silicone modified polyester resin, Effect of Organosilicon-modified Phenol-formaldehyde Resin, organosilicon-modified styrene-acrylic rubber, organic-silicon-modified butylbenzene rubber
At least one of glue.
It should be noted that term " organosilicon-modified acrylate system resin " in the present invention means that " organosilicon changes
The general designation of property methacrylate ester resin " and " organosilicon-modified acrylate system resin ".
The form of organic silicon-type material is not particularly limited.From the viewpoint of processability, in the present invention, organic silicon-type material
Material adds preferably in the form of organic silicon emulsion.In the case, the solid content of organic silicon emulsion is preferably 10-80 mass %,
More preferably 20-70 mass %, and more preferably 30-60 mass %.
For organic silicon-type material of the invention can be commercially available product, such as wacker chemicals manufactureEL 39、FF 230 VP、PN 100、CONCENTRATE、NFS、AE 54、AE 61、AE 66、PE 280、BS 1360、BS 16040 etc.；DOW CORNING manufacture MEM-0075, DC 349, IE-6683,
MEM-8194, Xiameter MEM-3422, Xiameter MEM-8031 etc.；WA-1, WS-3 of Shandong five lakes chemical industry manufacture,
ND7509 etc..
<pitch>
In the present invention, when using pitch in anticoagulant ice coating, have between anticoagulant ice coating and bituminous pavement
Excellent compatibility and the bituminous pavement after coating is made still to keep low key tone.In addition, being improved anti-due to the plasticity of pitch
The impact resistance of solidifying ice coating.
Type for the pitch in anticoagulant ice coating of the invention is not particularly limited, can be coal tar pitch, stone
Oil asphalt, bitumen and their various modified products.As modified product, can enumerate such as epoxy modified asphalt and
The resin modified asphalt of polyurethane-modified pitch etc., rubber modified asphalt such as styrene butadiene rubber modified asphalt etc..
Organosilicon from the impact resistance and hydrophobic viewpoint for improving anticoagulant ice coating simultaneously, relative to 100 mass parts
Based material, the content of pitch are 10-70 mass parts, preferably 15-60 mass parts, more preferably 20-50 mass parts.When pitch
When content is less than above range, cost tends to be excessive, and the impact resistance of anticoagulant ice coating tends to be deteriorated, the color of anticoagulant ice coating
Tended to shallowly reduce so as to cause the safety of bituminous pavement.When the content of pitch is greater than above range, anticoagulant ice coating
Hydrophobicity and abrasion performance tend to deteriorate.In addition, no matter pitch content it is excessive or too small can all make making for anticoagulant ice coating
Tend to reduce with the service life.
The form of pitch is not particularly limited, can be cut-back asphalt or emulsified asphalt etc..It is excellent from the viewpoint of processability
Choosing uses emulsified asphalt.Using emulsified asphalt, the solid content of emulsified asphalt is preferably 20-80 mass %, more excellent
It is selected as 30-70 mass %, and more preferably 40-60 mass %.
The properties of emulsified asphalt for use in the present invention preferably satisfy index shown in following table 1.
Table 1
Note: detection method is according to as defined in professional standard " highway engineering pitch and Asphalt Mixture Experiment regulation " IJGE20
Method executes.
<curing catalysts>
In the present invention, curing catalysts are used for so that anticoagulant ice crosslinking coatings solidify.Do not have to curing catalysts of the invention
It is particularly limited to, the example includes but not limited to organic titanic compound, such as tetraisopropoxy titanium, four tert-butoxy titaniums, two (isopropyls
Oxygroup) bis- (oacetic acid) titaniums, bis- (acetoacetyl acetic acid (the acetylacetoacetate)) titaniums of two (isopropoxies)；Have
Machine tin compound, such as dibutyl tin dilaurate, biacetyl acetoacetate dibutyl tin and tin octoate；Metal dicarboxylate,
Such as two lead octoates；Organic zirconate, such as four acetylacetone,2,4-pentanedione zirconiums；Organo-aluminum compound such as praseodynium aluminium；And amine, such as hydroxyl
Base amine and tri-butylamine.
Relative to the organic silicon-type material of 100 mass parts, the content of curing catalysts is 0.5-5.0 mass parts, preferably
0.8-4.5 mass parts, more preferably 1.0-4.0 mass parts.If the content of curing catalysts is very few, coating of the invention is consolidated
Change performance and tend to be insufficient, and is excessively used and tends to lead to storage stability loss.
<filler and silane coupling agent>
Anticoagulant ice coating of the invention can also include filler, to further increase the intensity and antiskid of anticoagulant ice coating
Performance.The example of filler of the invention includes but not limited to diamond dust, silica, carbon black, clay, mica, talcum, hard tree
Rouge particle etc..They can be used alone or are applied in combination with two or more.Organic silicon-type material relative to 100 mass parts
Material, the content of filler is preferably 5-40 mass parts, more preferably 10-30 mass parts.
Filler is preferably dimensioned to be 10-60 mesh, more preferably 20-50 mesh, and more preferably 24-45 mesh.
In the case where anticoagulant ice coating of the invention includes filler, anticoagulant ice coating can also include silane coupling agent,
To improve the compatibility between filler and organic silicon-type material and improve the dispersibility of filler.Silane coupling agent of the invention is
Known in the art, the example includes but not limited to vinyl three ('beta '-methoxy ethyoxyl) silane, γ-methacryloxy
Propyl trimethoxy silicane (KH-570), γ-methacryloxypropyl, γ-methacryloxy
Propyl tripropoxy silane, γ-methacryloxyethyl trimethoxy silane, three second of γ-methacryloxyethyl
Oxysilane, γ-methacryloxyethyl tripropoxy silane, β-(3,4- expoxycyclohexyl) ethyl trimethoxy silicon
Alkane, N- β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, gamma-amino propyl
Triethoxysilane (KH-550), gamma-amino propyl tripropoxy silane, γ mercaptopropyitrimethoxy silane (KH-590),
γ-Mercaptopropyltriethoxysilane, γ-mercaptopropyi tripropoxy silane, γ-(the third oxygen of 2,3- epoxy) hydroxypropyl methyl diformazan
Oxysilane, γ-(the third oxygen of 2,3- epoxy) hydroxypropyl methyl diethoxy silane, γ-(the third oxygen of 2,3- epoxy) hydroxypropyl methyl dipropyl
Oxysilane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane (KH-560), three second of γ-(the third oxygen of 2,3- epoxy) propyl
Oxysilane, γ-(the third oxygen of 2,3- epoxy) propyl tripropoxy silane, three isopropyl alkenyloxy group silicon of γ-epoxypropoxy propyl
The Michael of alkane, γ-glycidoxypropyl diisopropyl alkenyloxy group silane, (methyl) acryl silane and amino silane
Addition product, epoxy silane and reaction product of amino silane etc..
In order to preferably play the effect of silane coupling agent, the mass ratio (silane coupling agent/fill out of silane coupling agent and filler
Material) it is preferably 1/15-2/1, more preferably 1/10-1/1, more preferably 1/8-1/2.
<other additives>
Anticoagulant ice coating in the present invention can also further contain one kind or two or more thermal cross-linking agent, height as needed
Dispersal agent molecule, dispersing aid, curing accelerator, thickener, plasticizer, defoaming agent, levelling agent, antishrinking agent, ultraviolet light are inhaled
Receive other additives such as agent.
<preparation method of anticoagulant ice coating>
Anticoagulant ice coating of the invention can be by by organic silicon-type material, pitch, silane coupling agent, catalyst, this hair
Bright hud typed anticoagulant ice modifying agent and filler, silane coupling agent and above-mentioned other component mixing as needed and obtain.To structure
It is not particularly limited, and can be carried out using commonly known mixing machine at the order of addition of each component of anticoagulant ice coating
State mixing.
<solidification of anticoagulant ice coating>
The solidification temperature of anticoagulant ice coating of the invention is not particularly limited.Preferably, for the needs of outdoor construction, originally
The solidification of the anticoagulant ice coating of invention usually carries out at ambient temperature.
Embodiment
It will illustrate embodiment of the present invention by embodiment below, it is specific real but the present invention is not limited to these
Apply example.Unless otherwise indicated, term " part " means " mass parts ", and " % " means " quality % ".
Anticoagulant ice modifying agent is prepared in following Production Example.
Production Example 1
It weighs 4g industrial chlorinations sodium to be added in 100mL conical flask, 30mL dehydrated alcohol is added, then ultrasonic disperse 10min；
The dehydrated alcohol of the ammonium hydroxide and 10mL that measure 0.5mL with liquid-transfering gun is added in small beaker, is added in conical flask, stirs after evenly dispersed
It mixes and is uniformly dispersed；1.5mL tetraethyl orthosilicate is measured with liquid-transfering gun again and 10mL dehydrated alcohol is added in small beaker, after being uniformly dispersed
It is added in conical flask, closed container, reaction 12h is stirred at room temperature.After reaction, filtering, alcohol are washed, are dried, and obtain NaCl/SiO2
Core-shell Composite Particles.It is characterized using SEM.
Production Example 2
It weighs 4g industrial chlorinations sodium to be added in 100mL conical flask, 30mL dehydrated alcohol is added, then ultrasonic disperse 10min；
The dehydrated alcohol for measuring the deionized water of 1.0mL, 0.5mL ammonium hydroxide and 10mL is added in small beaker, and taper is added after evenly dispersed
In bottle, it is dispersed with stirring uniformly；1.5mL tetraethyl orthosilicate is measured with liquid-transfering gun again and 10mL dehydrated alcohol is added in small beaker, point
It is added in conical flask after dissipating uniformly, closed container, reaction 12h is stirred at room temperature.After reaction, filtering, alcohol are washed, are dried, and are obtained
NaCl/SiO2Compound particle.It is characterized using SEM.
Production Example 3
Other than measuring the deionized water of 2.0mL, NaCl/SiO is prepared in a manner of identical with Production Example 22Core
Shell compound particle.
Production Example 4
Other than measuring the deionized water of 3.0mL, NaCl/SiO is prepared in a manner of identical with Production Example 22Core
Shell compound particle.
Production Example 5
Other than measuring 1.0mL tetraethyl orthosilicate, NaCl/SiO is prepared in a manner of identical with Production Example 22Core
Shell compound particle.
Production Example 6
Other than measuring 2.0mL tetraethyl orthosilicate, NaCl/SiO is prepared in a manner of identical with Production Example 22Core
Shell compound particle.
Production Example 7
Other than measuring 0.2mL ammonium hydroxide, NaCl/SiO is prepared in a manner of identical with Production Example 22Nucleocapsid is compound
Particle.
Production Example 8
Other than measuring 1.5mL ammonium hydroxide, NaCl/SiO is prepared in a manner of identical with Production Example 22Nucleocapsid is compound
Particle.
Production Example 9
Other than measuring 0.5mL tetraethyl orthosilicate, NaCl/SiO is prepared in a manner of identical with Production Example 22Core
Shell compound particle.
Compare Production Example 1
4g industrial chlorinations sodium is mixed under heating with 5g silane resin acceptor kh-550, obtains silane coupling agent cladding
Anticoagulant ice modifying agent.
Compare Production Example 2
4g industrial chlorinations sodium is added to the water heating stirring, 2g zeolite is added after dissolution, is sufficiently mixed and evaporates whole
Moisture obtains zeolite-loaded anticoagulant ice modifying agent.
The coating for being prepared for each anticoagulant ice coating in the examples below and being formed by them.
Embodiment 1
It is that be added to 100 parts of solid contents be in 50% organic silicon emulsion with 200rpm to 50% emulsified asphalt by 40 parts of solid contents
Revolving speed stir 10min, the hud typed anticoagulant ice modifying agent prepared in 16 parts of Production Example 2 is added and is stirred with the revolving speed of 200rpm
3 parts of silane coupling agents are added in 15min, while 1.0 parts of dibutyl tin dilaurate is added and is stirred with the revolving speed of 300rpm
20min is eventually adding 10 part of 40 mesh diamond dust.Obtain the anticoagulant ice organosilicon coating of hydrophobic slow release.
Embodiment 2
In addition to the hud typed anticoagulant ice modifying agent in embodiment 1 is replaced with the hud typed anticoagulant ice prepared in Production Example 1
Other than modifying agent, organosilicon coating is obtained in the same manner as in example 1.
Embodiment 3
In addition to the hud typed anticoagulant ice modifying agent in embodiment 1 is replaced with the hud typed anticoagulant ice prepared in Production Example 9
Other than modifying agent, organosilicon coating is obtained in the same manner as in example 1.
Comparative example 1
In addition to by the hud typed anticoagulant ice modifying agent in embodiment 1 replace with the water-soluble metal salt not coated with
Outside, organosilicon coating is obtained in the same manner as in example 1.
Comparative example 2
Change in addition to the hud typed anticoagulant ice modifying agent in embodiment 1 is replaced with the anticoagulant ice for comparing and preparing in Production Example 1
Other than property, organosilicon coating is obtained in the same manner as in example 1.
Comparative example 3
Change in addition to the hud typed anticoagulant ice modifying agent in embodiment 1 is replaced with the anticoagulant ice for comparing and preparing in Production Example 2
Other than property, organosilicon coating is obtained in the same manner as in example 1.
Embodiment 4
Other than the dosage of the hud typed anticoagulant ice modifying agent in embodiment 1 is become 9 parts, with phase in embodiment 1
Same mode obtains organosilicon coating.
Comparative example 4
Other than the dosage of the hud typed anticoagulant ice modifying agent in embodiment 1 is become 4 parts, with phase in embodiment 1
Same mode obtains organosilicon coating.
Comparative example 5
Other than the dosage of the hud typed anticoagulant ice modifying agent in embodiment 1 is become 60 parts, with phase in embodiment 1
Same mode obtains organosilicon coating.
Embodiment 5
In addition to by the solid content in embodiment 1 be 50% emulsified asphalt dosage become 20 parts other than, with in embodiment 1
Identical mode obtains organosilicon coating.
Comparative example 6
In addition to by the solid content in embodiment 1 be 50% emulsified asphalt dosage become 80 parts other than, with in embodiment 1
Identical mode obtains organosilicon coating.
Comparative example 7
In addition to by the solid content in embodiment 1 be 50% emulsified asphalt dosage become 8 parts other than, with in embodiment 1
Identical mode obtains organosilicon coating.
Performance test
The hydrophobicity of anticoagulant ice modifying agent
Due to the surface of anticoagulant ice modifying agent and irregular, the present invention is anti-to test by following industrial common method
The hydrophobicity of solidifying ice modifying agent.
Step 1: taking out anticoagulant ice modifying agent and with taper heap in surface, depressed from conial vertex, by taper heap
Extrude smooth inner concave；
Step 2: removing ionized water with 0.5ml dropper and dripped water droplet by concave surface minimum point；
Step 3: the time that record water droplet is stopped in concave surface without penetrating into anticoagulant ice modifying agent.
For each Production Example and compare the anticoagulant ice agent in Production Example, is evaluated based on following standard, as a result in table 2
It shows.
◎: the residence time is 5min or more,
Zero: the residence time be less than 5min and 3min or more,
△: the residence time be less than 1min and 20 second or more,
×: the residence time is less than 20 seconds.
Table 2
The hydrophobicity of coating
Contact angle θ can be used in the hydrophobicity of the anticoagulant ice coating formed by the anticoagulant ice coating in each embodiment and comparative example
Size evaluated.Contact angle θ is measured by contact angle measurement.Specifically, anticoagulant ice coating is sprayed into glass
The surface of glass slide simultaneously solidifies to form anticoagulant ice coating, later, water droplet is dripped to uncoated glass slide and tool respectively
On the glass slide surface for having anticoagulant ice coating, the case where shooting photo, compare static contact angle.About each embodiment and ratio
Concrete outcome compared with the contact angle of the anticoagulant ice coating in example is shown in table 3.
Test results are shown in figure 4 for the coating of embodiment 1.Coating with embodiment 1 is formed by the load glass of coating
The contact angle of the drop of on piece is 95.6 °, and the contact angle of the drop on clean glass slide is 30 °.It can by data comparison
To obtain, coating of the invention has good hydrophobic performance.
Fig. 5 is shown when water droplet drips to uncoated prevailing roadway and with being formed by the anticoagulant ice coating of embodiment 1 respectively
Coating road surface on situation.As seen from Figure 5, anticoagulant ice coating of the invention has been obviously improved the hydrophobic anti-icing property on road surface
Energy.
The anticoagulant ice of coating
In the test of anticoagulant ice, tested according to following steps.It is noted that also being prepared not in a manner of approximate
Reference coating comprising anticoagulant ice modifying agent.
Step 1: wet wheel abrasion test specimen is made, wet wheel abrasion test specimen edge is sealed with plasticine, prevents water loss, it
Afterwards, by above-mentioned anticoagulant ice coating and with reference to coating application in surface of test piece.Wherein, the brushing amount of coating is to be easy to uniformly cover completely
Lid surface of test piece, fountain height when combining practice of construction are principle.The brushing amount of surface of test piece coating is 0.4-0.6kg/
m2。
Step 2: after paint solidification is with coating, simulating winter rainfall snowfall, added in surface of test piece a certain amount of
Water (amount of water is to be equivalent to the about primary middle sleet precipitation in an area).Then -15 DEG C of cryostat is placed it in
In, to simulate the climatic environment in winter.
Step 3: test specimen is taken out after 3 hours, the impact effect of simulated automotive tire road pavement gently taps ice sheet,
Then the cracking situation of ice sheet and the combination situation of ice cube and surface of test piece are observed.
Because the anticoagulant ice field reason of anticoagulant ice coating is by the combination between barrier ice sheet and road surface and to reduce freezing point,
Then ice sheet is crushed using the effect of traffic load, to reach deicing effect.Therefore, surface feelings of each test specimen by visual observation
Condition, based on after gently tapping ice sheet, whether ice sheet is easy the broken and degree that falls off from test specimen that cracks, and evaluates anticoagulant ice
Energy.
The deicing that Fig. 6 shows the coating formed by reference coating and the coating formed by the anticoagulant ice coating of embodiment 1 is imitated
Fruit.As shown in Figure 6, be formed with the surface of test piece of the coating with reference to coating and ice sheet bond it is unusually strong, even if gently tapping
Ice sheet is also closely knit afterwards, can not remove.As reference, evaluated based on following standard.
Zero: after percussion, ice sheet loose crushing is completely fallen off,
△: after percussion, ice sheet cracking is more, largely falls off,
×: after percussion, ice sheet cracking is less, and fall off difficulty.
The slow release of coating
The test of slow release is specific as follows.
Step 1: it is similar to the step 1 in the test of anticoagulant ice, the anticoagulant ice prepared in embodiment and comparative example is applied
Material is brushed on test specimen.
Step 2: after coating is dry with coating, simulating winter rainfall snowfall, added in surface of test piece a certain amount of
Water.Then water and test specimen are placed under conditions of -15 DEG C together.
Step 3: test specimen is taken out after 3 hours, the impact effect of simulated automotive tire road pavement gently taps ice sheet,
Then the cracking situation of ice sheet and the combination situation of ice cube and surface of test piece are observed.
Step 4: if ice sheet is frangible (level for reaching the △ or more in the test of anticoagulant ice), it is anticoagulant to illustrate that coating has
Ice effect then removes surface of test piece ice sheet, and repeat the above steps 1-3.
According to the number that can repeat test, evaluated based on following standard.
Zero: can be repeated 10 times it is above,
△: can repeat less than 10 times and 5 times or more,
×: it can be repeated 5 times following.
It is noted that, in order to meet the needs of winter, can be realized 5-6 circulation as art technology index
Test illustrates that technical effect is substantially better than current conventional technique if slow release test is able to carry out 10 times or more
Index.
Above-mentioned each test is carried out to anticoagulant ice modifying agent obtained in the various embodiments described above and comparative example, and evaluates knot
Fruit is shown in table 3 together.
Table 3
| Embodiment number | Contact angle (°) | Anticoagulant ice | Slow release |
| Embodiment 1 | 95.6 | ○ | ○ |
| Embodiment 2 | 95.2 | ○ | △ |
| Embodiment 3 | 93.0 | ○ | ○ |
| Comparative example 1 | 91.5 | ○ | × |
| Comparative example 2 | 92.4 | △ | × |
| Comparative example 3 | 91.5 | △ | × |
| Embodiment 4 | 95.4 | ○ | ○ |
| Comparative example 4 | 95.6 | × | × |
| Comparative example 5 | 96.4 | ○ | ○ |
| Embodiment 5 | 97.0 | ○ | ○ |
| Comparative example 6 | 89.2 | ○ | △ |
| Comparative example 7 | 97.9 | ○ | × |
As shown in table 3, there is excellent hydrophobicity, anticoagulant ice by meeting the coating that the embodiment of the present invention 1-5 is formed
Property and slow release.In addition, by meeting coating that the embodiment of the present invention 1-5 is formed in the test process for evaluating slow release
In, there is not apparent salt to be precipitated, and coating is also not affected by destruction, i.e., these coatings can be used for a long time.
As shown in table 3, although there is good hydrophobicity by meeting the coating that comparative example 1-3 of the invention is formed,
It is compared with effect of the invention, anticoagulant ice and slow release are poor.
The dosage of anticoagulant ice modifying agent in comparative example 4 is very few, therefore anticoagulant ice and slow release are poor.Although by comparative example
The coating that 5 coating is formed has good hydrophobicity, anticoagulant ice and slow release, still, due to the anticoagulant ice in comparative example 5
The dosage of modifying agent is excessive, carries out repeating to observe that surface of test piece has gradually appeared white when testing in the evaluation of slow release
Salt is precipitated, this will lead to the pollution in actual use to environment；In addition, being excessively used for anticoagulant ice agent will lead to cost mistake
It is high.
When emulsified asphalt excessive (comparative example 6), the binding force on coating and road surface is insufficient and hydrophobicity declines；And when emulsification
When pitch very few (comparative example 7), the resistance to external impacts of coating are insufficient.Therefore, slow release deterioration in both cases, makes
It is also deteriorated with the service life.
The embodiment above is just for the sake of clearly demonstrating made example, and not limitation of the present invention.For
For those of ordinary skill in the art, other different form variations can also be made on the basis of the above description or are become
It is dynamic.There is no need and unable to be exhaustive to all embodiments.And the obvious changes or variations therefore amplified
Within protection scope of the present invention.
Claims (9)
1. a kind of hud typed anticoagulant ice modifying agent, which is characterized in that it includes core and shell, and the core is water-soluble metal
Salt particle, the shell is formed by oxide particle and the shell coats the core；The shell with a thickness of 10nm
More than.
2. hud typed anticoagulant ice modifying agent according to claim 1, which is characterized in that the oxide particle is titanium dioxide
Silicon particle or titanium dioxide granule.
3. hud typed anticoagulant ice modifying agent according to claim 1 or 2, which is characterized in that the water-soluble metal salt is
At least one selected from sodium chloride, calcium chloride, magnesium chloride, calcium acetate, magnesium acetate, potassium acetate.
4. a kind of manufacturing method of hud typed anticoagulant ice modifying agent according to claim 1-3, which is characterized in that
Include:
It is dispersed in water-soluble metal salt in the alcohols solvent as initial dispersion medium, then addition alkalinity is urged thereto
Agent is optionally added deionized water, obtains pre-dispersed liquid；
Under stiring, it in Xiang Suoshu pre-dispersed liquid, adds the presoma of oxide particle and is reacted；
Solid component is obtained by filtration, and is washed and is dried.
5. manufacturing method according to claim 4, which is characterized in that the basic catalyst is selected from ammonium hydroxide, hydroxide
At least one of sodium, potassium hydroxide.
6. a kind of anticoagulant ice coating characterized by comprising relative to the organic silicon-type material of 100 mass parts, 10-70 mass
Part pitch, the curing catalysts of 0.5-5.0 mass parts, 10-55 mass parts core according to claim 1-3
The anticoagulant ice modifying agent of shell mould.
7. anticoagulant ice coating according to claim 6, which is characterized in that the organic silicon-type material is selected from organosilicon tree
Rouge, organic silicon modified polyurethane resin, modifying epoxy resin by organosilicon, organosilicon-modified acrylate system resin, fluorine richness
Organic siliconresin, silicone modified polyester resin, Effect of Organosilicon-modified Phenol-formaldehyde Resin, organosilicon-modified styrene-acrylic rubber, organosilicon change
At least one of property butadiene-styrene rubber.
8. anticoagulant ice coating according to claim 6 or 7, which is characterized in that it further includes filler.
9. anticoagulant ice coating according to claim 8, which is characterized in that it further includes silane coupling agent.
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