CN101863625B - Hydrophobic solution, hydrophobic glass for vehicle and manufacturing method thereof - Google Patents

Hydrophobic solution, hydrophobic glass for vehicle and manufacturing method thereof Download PDF

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Publication number
CN101863625B
CN101863625B CN200910106661A CN200910106661A CN101863625B CN 101863625 B CN101863625 B CN 101863625B CN 200910106661 A CN200910106661 A CN 200910106661A CN 200910106661 A CN200910106661 A CN 200910106661A CN 101863625 B CN101863625 B CN 101863625B
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Prior art keywords
glass
hydrophobic
vehicle
film layer
sol
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Expired - Fee Related
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CN200910106661A
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Chinese (zh)
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CN101863625A (en
Inventor
董清世
辛崇飞
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Dongguan is to fast vehicle glass company limited
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XINYI AUTO GLASS (DONGGUAN) CO Ltd
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Priority to CN200910106661A priority Critical patent/CN101863625B/en
Priority to PCT/CN2010/071643 priority patent/WO2010118667A1/en
Publication of CN101863625A publication Critical patent/CN101863625A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The invention belongs to the surface modification field of vehicle glass, and provides hydrophobic solution, a manufacturing method for hydrophobic glass for a vehicle and the hydrophobic glass for the vehicle. The hydrophobic solution consists of silane, silicate ester, alcohol, acid catalyst and stabilizing agent, wherein the number of carbon atoms of the silane is 10 to 18. The manufacturing method comprises the following steps of: coating the hydrophobic solution as claim 1 on the surface of a piece of glass to form a hydrophobic film layer, performing physical and chemical reaction on the glass, and thermally treating the glass to obtain the hydrophobic glass. The hydrophobic glass for the vehicle comprises the glass, the hydrophobic film layer formed by the hydrophobic solution is coated on the outer surface of the glass, and the contact angle of the hydrophobic film layer is more than 90 degrees. The silicate ester and the long-chain silane produce hydrolysis reaction under the condition of acid catalysis, and the generated hydrolysis product and a SiOH group on the surface of the fresh glass produce condensation polymerization reaction to form a firm silicon-oxygen chemical bond combination so as to improve the adhesion of the hydrophobic film layer and the glass.

Description

A kind of hydrophobic sol, vehicle are with Hydrophobic glass and method of manufacture thereof
Technical field
The invention belongs to the surface-treated field of vehicle glass, relate in particular to a kind of hydrophobic sol, vehicle with Hydrophobic glass and method of manufacture thereof.
Background technology
During vehicle was run at high speed in the rainy day, rainwater etc. can stick to windshield or back-mirror glass surface, had a strong impact on officer's sight line, even adopt wiper, also can leave a lot of dead angles.And it is just powerless for lateral Qianmen glass, two glass wipers.Point out that according to the expert in the time of when we drive, need making some very important decisions, eyes provide about 90% information reference.65% driver experiences the difficulty of driving when raining by day, and 82% people realizes the difficulty of rainy day at night driving.In the rainy day, road surface that mire skids and low-down visibility meter have caused the rate occurred frequently of traffic hazard.
In fact, the time can have a strong impact on driver's the visual field in unordered expansion on glass when raindrop.During the solution of coated with hydrophobic property on glass, the acuteness that can improve the driver is more than 34%, and the reaction times improves 25%, and this safety is improved especially to effective through the vehicle of driving over a long distance of the rainy weather operation of being everlasting.Existing Hydrophobic glass because hydrophobic sol adopts the oiliness physical attachment, comes off hydrophobic film layer easily, has influenced the hydrophobicity of Hydrophobic glass.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of hydrophobic film layer adhesion property good hydrophobic solution, vehicle made from Hydrophobic glass and method of manufacture thereof.
For a kind of hydrophobic sol; The embodiment of the invention is solved like this: this hydrophobic sol is that the stablizer of 0.5～8% silane, 1.0～5.0% silicon ester, 85～98% alcohol, 0.1～0.4% acid catalyst and 0.4～2.0% is formed by volume ratio, and the carbon atom of said silane is 10～18.
For the method for manufacture of a kind of vehicle with Hydrophobic glass; The embodiment of the invention is solved like this: apply a kind of hydrophobic sol as claimed in claim 1 at glass surface and form hydrophobic film layer; Through physical-chemical reaction, obtain said Hydrophobic glass through thermal treatment again.
Use Hydrophobic glass for a kind of vehicle, the embodiment of the invention is solved like this: it comprises glass, it is characterized in that: the outside surface of said glass is coated with one deck by the formed hydrophobic film layer of hydrophobic sol as claimed in claim 1.
Compared with prior art; The hydrophobic sol employing carbon atom that the embodiment of the invention provides is 10～18 a long chain silane; Silicon ester and long chain silane be the meeting hydrolytic reactions under the acidic catalyst condition, and polycondensation takes place for the hydrolysate of generation and the SiOH of fresh glass surface base, and the silica chemical bond that forms mortise combines; Extended the silicon-oxy tetrahedron network structure of glass; This combination is not simple physical adsorption, but a kind of chemical bond combines, and has improved the sticking power of hydrophobic film layer and glass.
The embodiment of the invention provides the method for manufacture of vehicle with Hydrophobic glass; With hydrophobic sol be coated on glass after; Make hydrophobic sol and glass generation physical-chemical reaction, the silica chemical bond that forms mortise combines, thereby it is on glass that hydrophobic film layer can finely be attached to.
The vehicle that the embodiment of the invention provides is used Hydrophobic glass; Behind coating adhesion property good hydrophobic rete on glass; The hydrophobic film layer surface has own ability in very low surface and superpower hydrophobic property; What show on the macroscopic view is exactly that the contact angle of glass surface obviously increases, and can reach more than 90 degree, has the good hydrophobic performance.Thereby make water droplet can not adhere to the surface and be round bead shape, and tumble outside glass under the air-flow that produces by deadweight or running car, wind effect.Like this, glass surface can keep clean vitreous state, and officer's the visual field is fully guaranteed, and the vehicle operational safety performance improves greatly.
Description of drawings
Fig. 1 is the structural representation of a kind of hydrophobic toughened glass of providing of the embodiment of the invention;
Fig. 2 is the structural representation of a kind of hydrophobic laminated glass of providing of the embodiment of the invention.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention will be solved, below in conjunction with accompanying drawing and embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The embodiment of the invention can be used for windscree for vehicle, side window glass, back windshield etc., can be used for automobile, train, aircraft, agricultural vehicle, mechanical car etc.
Embodiment provides a kind of hydrophobic sol, is that the stablizer of 0.5～8% silane, 1.0～5.0% silicon ester, 85～98% alcohol, 0.1～0.4% acid catalyst and 0.4～2.0% is formed by volume ratio, and the carbon atom of silane is 10～18.
Above-mentioned silane can be 17 fluorine decyl Trimethoxy silane (CF 3(CF 2) 7CH 2CH 2Si (OCH 3) 3), or ten trifluoro octyl triethyl silicane (CF 3(CF 2) 5C 2H 4Si (OC 2H 5) 3) or octyl triethoxyl silane ((CH 3(CH 2) 5C 2H 4Si (OC 2H 5) 3)).
Above-mentioned silicon ester is meant to have general formula Si (OR) 4Compound, R is a low alkyl group, can be methyl, ethyl, propyl group, sec.-propyl etc., commonly used have in tetraethoxy, methyl silicate, the positive silicic acid propyl ester any.
Above-mentioned alcohol can be in ethanol, propyl alcohol, Virahol, the butanols one or more.
Above-mentioned acid catalyst can be acetic acid or sulfuric acid or hydrochloric acid.
The aforementioned stable agent can be for containing the aqueous solution that volume ratio is 0～2.0% Glacial acetic acid min. 99.5.
Like this, silicon ester and long chain silane be (PH＜3) meeting hydrolytic reactions under the acidic catalyst condition, following equation:
Si(OR) 4+4H 2O→Si(OH) 4+4ROH (PH＜3) (1)
R fSi(OR’) 3+3H 2O→R fSi(OH) 3+3R’OH(PH＜3) (2)
Wherein R, R ' are low alkyl group, can be CH 3Or CH 3CH 2Or CH 3CH 2CH 2, R fBe long chain alkyl group.
Polycondensation takes place in hydrolysate that reaction (1) and (2) generates and the SiOH of fresh glass surface base; The silica chemical bond that forms mortise combines; Extended the silicon-oxy tetrahedron network structure of glass; This combination is not simple physical adsorption, but a kind of chemical bond combines, and has improved the sticking power of rete and glass.The other end of long chain silane is the fluothane group [R with hydrophobic property fSiO-], the C-F key is difficult for polarization, and the Van der Waals force of C-F is littler than C-H; And the fluorine atom radius is big than Wasserstoffatoms; Can carbon atom be covered fully, and make carbon fluorine molecule gravitation very little, cause fluorochemical surfactant littler than hydrocarbon polymer surface tension; Have the own ability in very low surface, promptly form R with hydrophobic property at glass surface fLong molecular chain is shown in reaction (3).
Figure G2009101066611D00041
A kind of vehicle that the embodiment of the invention provides is with the method for manufacture of Hydrophobic glass; Glass surface in clean; Be coated with above-mentioned hydrophobic sol, the hydrophobic film layer thickness of formation is between 100～500nm, through 3～10 minutes physical-chemical reaction; Be 80～250 ℃ through temperature again, obtain Hydrophobic glass thereby the time is 5～30 minutes thermal treatment.Like this, with hydrophobic sol be coated on glass after, make hydrophobic sol and glass generation physical-chemical reaction, the silica chemical bond that forms mortise combines, thereby it is on glass that hydrophobic film layer can finely be attached to.
This glass is toughened glass or laminated glass, and hydrophobic film layer is used for toughened glass or laminated glass outer plate outside surface, and wherein toughened glass applies hydrophobic sol again and carries out subsequent handling and handle behind tempering, and its thickness can be 2.0～8.0mm; And laminated glass is behind interlayer high pressure or outer plate glass bending, to carry out, and ECDC sheet, gummed, high pressure obtain again, and its thickness can be 4.0～12mm.
The coating method of above-mentioned hydrophobic sol can be methods such as spraying, roller coat, printing, polishing, makes hydrophobic film layer thickness at 100～500nm.
See also Fig. 1 and Fig. 2, the embodiment of the invention provides a kind of vehicle to use Hydrophobic glass, comprises glass 1, and the outside surface of glass 1 is coated with one deck by the formed hydrophobic film layer 2 of above-mentioned hydrophobic sol, and the contact angle M of hydrophobic film layer 2 is greater than 90 degree.
The thickness of above-mentioned hydrophobic film layer 2 is 100nm～500nm, makes hydrophobic film layer 2 reach nanometer grade thickness.
Above-mentioned glass 1 can be toughened glass or laminated glass outer plate equally, and the thickness of toughened glass can be 2.0～8.0mm; And the thickness of laminated glass can be 4.0～12mm.
Therefore; The vehicle that the present technique scheme provides is used Hydrophobic glass, through at windshield glass of automobile, side window glass surface applied one deck high-density, firm nano level tensio-active agent, make adhesion property good hydrophobic rete 2 surfaces have very low surface own can and superpower hydrophobic property; What show on the macroscopic view is exactly after water droplet 4 falls within glass 1 surface; Glass 1 obviously increases with the contact angle M of water droplet, can reach more than 90 °, has the good hydrophobic performance.Thereby make water droplet can not adhere to the surface and be round bead shape, and tumble outside glass under the air-flow that produces by deadweight or running car, wind effect.Like this, glass 1 surface can keep clean vitreous state, and officer's the visual field is fully guaranteed, and the vehicle operational safety performance improves greatly.
Specific embodiment one
1, the configuration of hydrophobic sol
According to 17 fluorine decyl Trimethoxy silanes 10%, tetraethoxy 10%, the volume ratio of propyl alcohol 80% configuration A solution; Volume ratio configuration solution B according to hydrochloric acid 0.8%, stablizer 2.0% (containing 0.2% Glacial acetic acid min. 99.5), propyl alcohol 97.2%; Again A, B solution equal-volume are mixed, stir and left standstill 10 hours, obtain hydrophobic sol.The volume of hydrophobic sol consists of: 17 fluorine decyl Trimethoxy silanes 5%, tetraethoxy 5%, propyl alcohol 88.6%, hydrochloric acid 0.4%, stablizer 1.0%.
2, the preparation technology of Hydrophobic glass
Glass through the glass cleaning machine cleaning; After the infrared drier oven dry; The mode that adopts the spraying of Japanese rock field spray gun forms the rete of one deck even compact at glass surface, through from thermal treatment 30 minutes on 80～100 ℃ drying line again behind the levelling, obtains Hydrophobic glass.Measure through contact angle measurement, the aqueous solution can reach 102 ° to the contact angle of glass.
Specific embodiment two
1, the configuration of hydrophobic sol
According to ten trifluoro octyl triethyl silicanes 4%, methyl silicate 2%, the volume ratio configuration C solution of ethanol 94%; According to acetic acid 0.2%, stablizer 4.0%, the volume ratio configuration solution D of alcohol 95 .8%; Again C, D solution equal-volume are mixed, stir and left standstill 2 hours, obtain hydrophobic sol.The volume of hydrophobic sol consists of: ten trifluoro octyl triethyl silicanes 2%, methyl silicate 1%, ethanol 94.9%, acetic acid 0.1%, stablizer 2.0% (containing 0.1% Glacial acetic acid min. 99.5).
2, the preparation technology of Hydrophobic glass
Glass through glass cleaning machine cleans after the infrared drier oven dry, adopts the surface deposition layer of even rete of the method for roller coating machine roller coat at glass, through from thermal treatment 20 minutes on 150～160 ℃ drying line behind the levelling, obtains Hydrophobic glass.Measure through contact angle measurement, the aqueous solution can reach 104 ° to the contact angle of glass.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (9)

1. hydrophobic sol; By volume ratio is that the stablizer of 0.5～8% silane, 1.0～5.0% silicon ester, 85～98% alcohol, 0.1～0.4% acid catalyst and 0.4～2.0% is formed; The carbon atom of said silane is 10～18, and said stablizer is to contain the aqueous solution that volume ratio is 0.2%～2.0% Glacial acetic acid min. 99.5.
2. hydrophobic sol as claimed in claim 1 is characterized in that: said silane is 17 fluorine decyl Trimethoxy silanes, or ten trifluoro octyl triethyl silicane, perhaps octyl triethoxyl silanes.
3. hydrophobic sol as claimed in claim 1 is characterized in that: said silicon ester is tetraethoxy or methyl silicate, or positive silicic acid propyl ester.
4. hydrophobic sol as claimed in claim 1 is characterized in that: said alcohol is one or more in ethanol, propyl alcohol, Virahol, the butanols.
5. hydrophobic sol as claimed in claim 1 is characterized in that: said acid catalyst is acetic acid or sulfuric acid or hydrochloric acid.
6. a vehicle applies a kind of hydrophobic sol as claimed in claim 1 at glass surface and forms hydrophobic film layer with the method for manufacture of Hydrophobic glass, through physical-chemical reaction, obtains said Hydrophobic glass through thermal treatment again.
7. a vehicle is used Hydrophobic glass, comprises glass, it is characterized in that: the outside surface of said glass is coated with one deck by the formed hydrophobic film layer of hydrophobic sol as claimed in claim 1.
8. vehicle as claimed in claim 7 is used Hydrophobic glass, it is characterized in that: the thickness of said hydrophobic film layer is 100nm～500nm.
9. vehicle as claimed in claim 8 is used Hydrophobic glass, it is characterized in that: said glass is toughened glass or laminated glass.
CN200910106661A 2009-04-17 2009-04-17 Hydrophobic solution, hydrophobic glass for vehicle and manufacturing method thereof Expired - Fee Related CN101863625B (en)

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PCT/CN2010/071643 WO2010118667A1 (en) 2009-04-17 2010-04-09 Hydrophobic solution, hydrophobic glass for vehicle and production method thereof

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CN102351437B (en) * 2011-08-01 2013-12-25 程道远 Glass after-mildew restoration agent
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CN106854042B (en) * 2016-12-19 2019-12-20 张新立 Preparation method of super-hydrophobic glass surface treating agent
CN106833043A (en) * 2017-02-27 2017-06-13 超为科技（北京）有限公司 A kind of transparent durable super-hydrophobic new material coating and preparation method thereof
CN107629492B (en) * 2017-09-11 2019-10-11 东南大学 The preparation method and its gained coating of a kind of super hydrophobic coating and the application for preparing high transparency super-hydrophobic coat
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CN1325416C (en) * 2005-10-14 2007-07-11 浙江大学 Glass hydrophobic film coating liuqid
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Address after: 523000, East Village, Humen Town, Dongguan, Guangdong

Patentee after: Dongguan is to fast vehicle glass company limited

Address before: 523935 Higashimura Nobuyoshironobuyoshi Glass Industrial Zone, Humen Town, Guangdong, Dongguan

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