CN108975722A - A kind of hydrophobic automobile adhesive film and preparation method thereof - Google Patents
A kind of hydrophobic automobile adhesive film and preparation method thereof Download PDFInfo
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- CN108975722A CN108975722A CN201810592012.6A CN201810592012A CN108975722A CN 108975722 A CN108975722 A CN 108975722A CN 201810592012 A CN201810592012 A CN 201810592012A CN 108975722 A CN108975722 A CN 108975722A
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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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D189/00—Coating compositions based on proteins; Coating compositions based on derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/29—Mixtures
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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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of hydrophobic automobile adhesive film and preparation method thereof, the following steps are included: the adhesive of mixed liquor, 20 parts by weight, the diethanol amine of 2 ~ 5 parts by weight, the potassium peroxydisulfate of 0.4 ~ 0.8 parts by weight, the stabilizer of 0.5 ~ 1.5 parts by weight by 30 ~ 40 parts by weight containing Nano particles of silicon dioxide and the mixing of the glycerol of 0.5 ~ 1.0 parts by weight, then 15 ~ 20min is dispersed continuously with 600 ~ 800r/min of revolving speed using dispersion machine, 45 ~ 60min of standing and defoaming, obtains coating；The surface of glass baseplate after coating to be coated in plasma treatment, the glass baseplate for being then coated with coating dry 2 ~ 3h at 45 ~ 60 DEG C, obtain porous gel film；Zeins liquid and the drying for spraying various concentration stage by stage to the surface of porous gel film, obtain hydrophobic automobile adhesive film.Hydrophobic automobile adhesive film of the invention has excellent translucency and hydrophobicity.
Description
Technical field
The present invention relates to automobile adhesive film fields more particularly to a kind of hydrophobic automobile adhesive film and preparation method thereof.
Background technique
Silicate glass surface is high energy, water-wetted surface, and at unordered extension on glass glass transmission can become water droplet
Difference brings many inconvenience to people's life and work.For automobile when running at high speed the rainy day, rainwater and muddy water are often sticked to windscreen
Glass or back-mirror glass surface, seriously affect pilot's line of vision, can there is many dead angles using wiper, increase thing
Therefore probability.For side window and rearview mirror, wiper is then helpless.
Hydrophobic film layer can prevent rainwater in its surface spreading, and water droplet is in spherical crown shape on surface, can tumble from surface rapidly,
Have the function of easy to clean simultaneously, can inhibit dirt in its surface adhesion.Bionic super-hydrophobic film is mainly by coarse table at present
Face modification low-surface energy substance is realized with the roughness two ways for improving low-surface energy substance.But the transparency and roughness
It is two factors vied each other, controls suitable surface roughness, is current to reach preferable film transparent (light transmittance)
The Research Challenges in the field.Though currently, occurring Motor Maintenance nano-glass rain-proof coated product, hydrophobic effect in the market
Fruit is bad, and preferably then transparency is low and durability is poor for hydrophobic effect.
Summary of the invention
In view of this, a kind of good the purpose of the present invention is to provide hydrophobic effect and high transparency hydrophobic automobile adhesive film and
Preparation method.
To achieve the goals above, the technical solution adopted by the present invention one are as follows:
A kind of preparation method of hydrophobic automobile adhesive film, comprising the following steps:
Step 1: ethyl orthosilicate and silane coupling agent being added into normal propyl alcohol and stirs 20 ~ 30min, is subsequently added into hexamethyl two
Silicon amine alkane continues 20 ~ 30min of stirring, and deionized water is then added dropwise, then is placed under 35 ~ 45 DEG C of water bath conditions and is stirred to react 4 ~ 12h,
Obtain the mixed liquor containing Nano particles of silicon dioxide, wherein the mass ratio of normal propyl alcohol, ethyl orthosilicate and silane coupling agent is 80
~ 100: 3 ~ 5: 0.2, the dosage of deionized water is the 10% of normal propyl alcohol quality；
Step 2: the corn alcohol for being equivalent to ethanol solution quality 10 ~ 12% being added in the ethanol solution for being 96 ~ 98% to volumetric concentration
Molten albumen simultaneously stirs 20 ~ 30min, obtains the first zeins liquid；Add in the ethanol solution for being 60 ~ 70% to volumetric concentration
Enter to be equivalent to the zeins of ethanol solution quality 1 ~ 3% and stir 10 ~ 20min, obtains the second zeins liquid；
Step 3: by the mixed liquor containing Nano particles of silicon dioxide of the step 1 of 30 ~ 40 parts by weight, the adhesive of 20 parts by weight, 2
The diethanol amine of ~ 5 parts by weight, the potassium peroxydisulfate of 0.4 ~ 0.8 parts by weight, the stabilizer of 0.5 ~ 1.5 parts by weight and 0.5 ~ 1.0 weight
Part glycerol mixing, 15 ~ 20min is then dispersed continuously with 600 ~ 800r/min of revolving speed using dispersion machine, standing and defoaming 45 ~
60min obtains coating；
Step 4: plasma treatment is carried out to glass baseplate, the coating then prepared step 3 by spin coater be coated in it is equal from
The surface of glass baseplate after subprocessing, the glass baseplate for being then coated with coating are dried 2 ~ 3h at 45 ~ 60 DEG C, are obtained more
Hole gel mould；
Step 5: to the first zeins liquid of the surface spraying process 2 of the porous gel film of step 4, it is subsequently placed in 45 ~
Dry 2 ~ 3h at 60 DEG C, then the second zeins liquid of spraying process 2, continue to be placed at 45 ~ 60 DEG C continue dry 4 ~
6h obtains hydrophobic automobile adhesive film；
Wherein, described adhesive is grouped as by following each group by mass percentage: the ethanol solution that volumetric concentration is 70%
10%, ethyl acetate 32%, ethyl acrylate 20%, zeins 18%, methyl acrylate 12%, methacrylic acid 5%, amino
Silane coupling agent 2%, hydroxy stearic acid 0.5%, benzoyl peroxide 0.3% and lauryl mercaptan 0.2%.
The key ideas of above-mentioned technical proposal one is: the present invention passes through using above-mentioned containing Nano particles of silicon dioxide
Adhesive that mixed liquor and the various of monomer similar in refraction coefficient aggregate into simultaneously is aided with above-mentioned auxiliary material and constructs with certain table
The porous gel film of surface roughness, then spray the zeins liquid of two kinds of various concentrations with formed simulation lotus leaf it is super-hydrophobic micro-
The film pattern of structure, and then obtain high transparency and the good automobile adhesive film of hydrophobicity.
Further, the silane coupling agent of the step 1 is a kind of in KH570 or KH560.
Further, described adhesive is made by following preparation method: volumetric concentration is added in zeins
To stir 10 ~ 20min in 30 ~ 45 DEG C of water bath, obtaining the first mixture in 70% ethanol solution；By acrylic acid second
Ester, methyl acrylate, methacrylic acid, lauryl mercaptan and benzoyl peroxide are mixed into the second mixture；Second will be accounted for
Second mixture of mixture gross mass 4/5 forms reaction system after mixing with the ethyl acetate for accounting for ethyl acetate gross mass 2/3,
Reaction system is warming up to 65 ~ 70 DEG C, keeps the temperature 1 ~ 2h, is then added dropwise to remaining second mixture in 30 ~ 60min described
Reaction system after being added dropwise, then by remaining ethyl acetate addition reaction system, is warming up to 72 ~ 75 DEG C, keeps the temperature 1 ~ 2h, connect
Be cooled to 30 ~ 45 DEG C, the first mixture, hydroxy stearic acid and amino silicane coupling agent is added, stirs 20 ~ 30min, discharging,
Obtain described adhesive.
Further, the dosage of first zeins liquid is 30 ~ 40% of coating quality in step 3 in step 5.
Further, the dosage of second zeins liquid is 50 ~ 60% of coating quality in step 3 in step 5.
Further, the concrete operations of step 5 are as follows: with pressure be 50psi air cannon using vertical and horizontal alternate mode to
First zeins liquid of the surface spraying process 2 of the porous gel film of step 4, it is subsequently placed at 45 ~ 60 DEG C dry 2 ~
3h then uses the second zeins liquid of vertical and horizontal alternate mode spraying process 2 with the air cannon that pressure is 70psi,
Continue to be placed at 45 ~ 60 DEG C and continue dry 4 ~ 6h, obtains hydrophobic automobile adhesive film.
The beneficial effect of above-mentioned technical proposal one is: (1) present invention is received using the above-mentioned silica containing hydrophobic grouping
Adhesive that the mixed liquor of rice corpuscles and the various of monomer similar in refraction coefficient aggregate into simultaneously is aided with above-mentioned auxiliary material building and provides
There is the porous gel film of certain surface roughness, then sprays the zeins liquid of two kinds of various concentrations to form simulation lotus leaf
The film pattern of superhydrophobic microstructure, and then obtained high transparency and the good automobile adhesive film of hydrophobicity；(2) automobile of the invention patch
The adhesive of film uses ethyl acrylate, methyl acrylate similar in refraction coefficient and methacrylic acid to be polymerize for monomer,
The transparency finally to form a film is further improved, the light transmittance of film is further improved；(3) adhesive that the present invention uses is forgone
The presence of double bond or phenyl ring in polymer, improves the weatherability of adhesive itself, and nano SiO 2 particle is led to
It crosses sufficiently to be uniformly dispersed and is embedded in adhesive and other auxiliary materials and plasma treatment is carried out in conjunction with coating to glass baseplate
Mode is once completed to coat, and constructs the porous gel film with certain surface roughness in advance, effectively increases film layer and base
The binding force at bottom, and can effectively prevent falling off for silicon dioxide granule, therefore also substantially increase the durability of automobile adhesive film；
(4) adjustment that the present invention passes through above-mentioned technique, it is ensured that the compactness of the automobile adhesive film of preparation further improves its transparency
Its heat-proof quality is improved again.
To achieve the goals above, the technical solution adopted by the present invention two are as follows:
A kind of hydrophobic automobile adhesive film prepared according to above-mentioned preparation method.
The beneficial effect of above-mentioned technical proposal two is: automobile adhesive film of the invention while having excellent hydrophobic performance, thoroughly
Photosensitiveness and durability.
Specific embodiment
It is as follows that the present invention is described further combined with specific embodiments below:
A kind of preparation method of hydrophobic automobile adhesive film provided by the invention, comprising the following steps:
Step 1: ethyl orthosilicate and silane coupling agent being added into normal propyl alcohol and stirs 20 ~ 30min, is subsequently added into hexamethyl two
Silicon amine alkane continues 20 ~ 30min of stirring, and deionized water is then added dropwise, then is placed under 35 ~ 45 DEG C of water bath conditions and is stirred to react 4 ~ 12h,
Obtain the mixed liquor containing Nano particles of silicon dioxide, wherein the mass ratio of normal propyl alcohol, ethyl orthosilicate and silane coupling agent is 80
~ 100: 3 ~ 5: 0.2, the dosage of deionized water is the 10% of normal propyl alcohol quality；
Step 2: the corn alcohol for being equivalent to ethanol solution quality 10 ~ 12% being added in the ethanol solution for being 96 ~ 98% to volumetric concentration
Molten albumen simultaneously stirs 20 ~ 30min, obtains the first zeins liquid；Add in the ethanol solution for being 60 ~ 70% to volumetric concentration
Enter to be equivalent to the zeins of ethanol solution quality 1 ~ 3% and stir 10 ~ 20min, obtains the second zeins liquid；
Step 3: by the mixed liquor containing Nano particles of silicon dioxide of the step 1 of 30 ~ 40 parts by weight, the adhesive of 20 parts by weight, 2
The diethanol amine of ~ 5 parts by weight, the potassium peroxydisulfate of 0.4 ~ 0.8 parts by weight, the stabilizer of 0.5 ~ 1.5 parts by weight and 0.5 ~ 1.0 weight
Part glycerol mixing, 15 ~ 20min is then dispersed continuously with 600 ~ 800r/min of revolving speed using dispersion machine, standing and defoaming 45 ~
60min obtains coating；
Step 4: plasma treatment is carried out to glass baseplate, the coating then prepared step 3 by spin coater be coated in it is equal from
The surface of glass baseplate after subprocessing, the glass baseplate for being then coated with coating are dried 2 ~ 3h at 45 ~ 60 DEG C, are obtained more
Hole gel mould；
Step 5: to the first zeins liquid of the surface spraying process 2 of the porous gel film of step 4, it is subsequently placed in 45 ~
Dry 2 ~ 3h at 60 DEG C, then the second zeins liquid of spraying process 2, continue to be placed at 45 ~ 60 DEG C continue dry 4 ~
6h obtains hydrophobic automobile adhesive film；
Wherein, described adhesive is grouped as by following each group by mass percentage: the ethanol solution that volumetric concentration is 70%
10%, ethyl acetate 32%, ethyl acrylate 20%, zeins 18%, methyl acrylate 12%, methacrylic acid 5%, amino
Silane coupling agent 2%, hydroxy stearic acid 0.5%, benzoyl peroxide 0.3% and lauryl mercaptan 0.2%.
Specifically, working principle of the present invention is as follows:
The present invention passes through above-mentioned technique direct hydrolysis anamorphic zone using ethyl orthosilicate, silane coupling agent and hexamethyldisilazane
There is the Nano particles of silicon dioxide of methacrylate (hydrophobic grouping), effectively enhances the hydrophobicity of silicon dioxide granule, and
And the partial size of the silica as made from above-mentioned technique is between 40 ~ 70nm, in addition with acrylic acid second similar in refraction coefficient
Ester, methyl acrylate and methacrylic acid are aided with zeins and polymerize to form above-mentioned special adhesive, by silica
Nano particle is uniformly embedded into adhesive and other auxiliary materials by fully dispersed, and the two is combined to effectively increase and finally be formed a film
Transparency (light transmittance), also improves the binding force of film layer and substrate, to improve the durability of automobile adhesive film, is formed simultaneously
Porous gel film have certain surface roughness and low-surface-energy, therefore have certain hydrophobicity；And at the same time, lead to
The solvent strength and protein concentration of zeins liquid are overregulated, to adjust out the zeins liquid of various concentration, hair
Bright people studies discovery zeins will form the particle of different-grain diameter size in the ethanol water of various concentration, when
For concentration of alcohol at 96 ~ 98%, grain diameter is larger, and then will form lesser particle in 60 ~ 70% ethanol solution, then divide
Stage sprays on porous gel film, and ethyl alcohol for water with respect to being easier to evaporate in drying process, therefore, in drying process corn alcohol
Molten protein body constantly assembles " self assembly ", so protein concentration determines the pattern on the surface of last film, first spraying contains
There is the zeins liquid of bulky grain to spray more short grained zeins liquid again, such little particle is easier to be embedded into big
In gap between particle, to form the film pattern like lotus leaf superhydrophobic microstructure, and then dredging for automobile adhesive film is further increased
Aqueous and toughness, thus obtain fabulous hydrophobicity of the invention, high transparency and the strong automobile adhesive film of durability.
As can be seen from the above description, the invention has the following advantages: (1) present invention is using above-mentioned containing hydrophobic grouping
Adhesive that the mixed liquor of Nano particles of silicon dioxide and the various of monomer similar in refraction coefficient aggregate into simultaneously is aided with above-mentioned auxiliary
Material constructs the porous gel film with certain surface roughness, then sprays the zeins liquid of two kinds of various concentrations with shape
At the film pattern of simulation lotus leaf superhydrophobic microstructure, and then high transparency and the good automobile adhesive film of hydrophobicity are obtained；(2) this hair
The adhesive of bright automobile adhesive film uses ethyl acrylate, methyl acrylate similar in refraction coefficient and methacrylic acid for monomer
It is polymerize, further improves the transparency finally to form a film, further improves the light transmittance of film；(3) present invention uses
Adhesive obviates the presence of double bond or phenyl ring in polymer, improves the weatherability of adhesive itself, and by silica
Nano particle by it is fully dispersed be uniformly embedded into adhesive and other auxiliary materials and to glass baseplate carry out plasma treatment again
It once completes to coat in conjunction with the mode of coating, constructs the porous gel film with certain surface roughness in advance, effectively improve
The binding force of film layer and substrate, and can effectively prevent falling off for silicon dioxide granule, therefore also substantially increase automobile adhesive film
Durability；(4) adjustment that the present invention passes through above-mentioned technique, it is ensured that the compactness of the automobile adhesive film of preparation further increases
Its transparency improves its heat-proof quality again.
Further, the silane coupling agent of the step 1 is a kind of in KH570 or KH560.
Further, described adhesive is made by following preparation method: volumetric concentration is added in zeins
To stir 10 ~ 20min in 30 ~ 45 DEG C of water bath, obtaining the first mixture in 70% ethanol solution；By acrylic acid second
Ester, methyl acrylate, methacrylic acid, lauryl mercaptan and benzoyl peroxide are mixed into the second mixture；Second will be accounted for
Second mixture of mixture gross mass 4/5 forms reaction system after mixing with the ethyl acetate for accounting for ethyl acetate gross mass 2/3,
Reaction system is warming up to 65 ~ 70 DEG C, keeps the temperature 1 ~ 2h, is then added dropwise to remaining second mixture in 30 ~ 60min described
Reaction system after being added dropwise, then by remaining ethyl acetate addition reaction system, is warming up to 72 ~ 75 DEG C, keeps the temperature 1 ~ 2h, connect
Be cooled to 30 ~ 45 DEG C, the first mixture, hydroxy stearic acid and amino silicane coupling agent is added, stirs 20 ~ 30min, discharging,
Obtain described adhesive.
As can be seen from the above description, the adhesive of the invention is mentioned by selecting above-mentioned raw material and by the adjustment of polymerization technique
The molecular weight of adhesive is risen, so that the molecular weight of final adhesive reaches 600000 ~ 650000, such is average than existing market
Adhesive of the molecular weight between 200000 ~ 500000 greatly improves, and the adhesive coefficient of dispersion is small, ensure that film forming
Compactness further improves the transparency (light transmittance) of final automobile adhesive film, meanwhile, improve the adhesive tension of adhesive.
Further, the dosage of first zeins liquid is 30 ~ 40% of coating quality in step 3 in step 5.
Further, the dosage of second zeins liquid is 50 ~ 60% of coating quality in step 3 in step 5.
Seen from the above description, by the solvent strength of the first and second zeins liquid and protein concentration and dosage, to fill
Dividing using zeins is that porous gel film is surface modified, and it is final to further strengthen film the case where influencing transparency
Hydrophobicity.
Further, the concrete operations of step 5 are as follows: with pressure be 50psi air cannon using vertical and horizontal alternate mode to
First zeins liquid of the surface spraying process 2 of the porous gel film of step 4, it is subsequently placed at 45 ~ 60 DEG C dry 2 ~
3h then uses the second zeins liquid of vertical and horizontal alternate mode spraying process 2 with the air cannon that pressure is 70psi,
Continue to be placed at 45 ~ 60 DEG C and continue dry 4 ~ 6h, obtains hydrophobic automobile adhesive film.
Seen from the above description, it according to the difference of the concentration of zeins liquid, is adopted using the air cannon of different pressures
It is sprayed with vertical and horizontal alternate mode, facilitates zeins liquid and be uniformly coated in porous gel film surface, simultaneously
It is first dried before the spraying of the second zeins liquid, the second zein liquid is avoided to cause the first zein liquid
Dilution, it helps keep the clarity of film layer.
Several preferred embodiments or Application Example are enumerated, again below to help those skilled in the art to better understand
The technical contribution that technology contents and the present invention of the invention are made compared with the existing technology:
The preparation of preparation example 1(invention adhesives)
Adhesive is grouped as by following each group by mass percentage: volumetric concentration be 70% ethanol solution 10%, acetic acid second
Ester 32%, ethyl acrylate 20%, zeins 18%, methyl acrylate 12%, methacrylic acid 5%, amino silicane coupling agent
2%, hydroxy stearic acid 0.5%, benzoyl peroxide 0.3% and lauryl mercaptan 0.2%；
Described adhesive is made by following preparation method: volumetric concentration is added in zeins (zeins)
To stir 15min in 40 DEG C of water bath, obtaining the first mixing in 70% ethanol solution (volumetric concentration of ethyl alcohol is 50%)
Object；Ethyl acrylate, methyl acrylate, methacrylic acid, lauryl mercaptan and benzoyl peroxide are mixed into second to mix
Close object；After the second mixture for accounting for the second mixture gross mass 4/5 is mixed with the ethyl acetate for accounting for ethyl acetate gross mass 2/3
Reaction system is formed, reaction system is warming up to 68 DEG C, 1.5h is kept the temperature, then drips remaining second mixture in 45min
The reaction system is added, after being added dropwise, then by remaining ethyl acetate addition reaction system, is warming up to 74 DEG C, heat preservation
1.5h is then cooled to 35 DEG C or so, and the first mixture, hydroxy stearic acid and amino silicane coupling agent is added, and stirs 25min,
Discharging, obtains described adhesive.
Embodiment 1
A kind of preparation method of hydrophobic automobile adhesive film, comprising the following steps:
Step 1: ethyl orthosilicate and silane coupling agent being added into normal propyl alcohol and stirs 20min, is subsequently added into two silicon of hexamethyl
Amine alkane continues to stir 20min, deionized water is then added dropwise, then be placed under 35 DEG C of water bath conditions and be stirred to react 4h, obtains containing dioxy
The mixed liquor of SiClx nanoparticle (partial size 42nm), wherein the mass ratio of normal propyl alcohol, ethyl orthosilicate and silane coupling agent is
80: 3: 0.2, the dosage of deionized water is the 10% of normal propyl alcohol quality；
Step 2: the zeins for being equivalent to ethanol solution quality 10% being added in the ethanol solution for being 96% to volumetric concentration
And 20min is stirred, obtain the first zeins liquid；It is added in the ethanol solution for being 60% to volumetric concentration and is equivalent to ethyl alcohol
The zeins of solution quality 1% simultaneously stirs 10min, obtains the second zeins liquid；
Step 3: by the mixed liquor containing Nano particles of silicon dioxide of the step 1 of 30g, the adhesive of 20g, 2g diethanol amine,
The glycerol of the potassium peroxydisulfate of 0.4g, the stabilizer of 0.5g and 0.5g mixes, then continuous with revolving speed 600r/min using dispersion machine
Disperse 15min, standing and defoaming 45min obtains coating；
Step 4: plasma treatment is carried out to glass baseplate, the coating then prepared step 3 by spin coater be coated in it is equal from
The surface of glass baseplate after subprocessing, the glass baseplate for being then coated with coating dry 2h at 45 DEG C, obtain porous solidifying
Glue film；
Step 5: spraying on the surface of porous gel film of the air cannon for being 50psi with pressure using vertical and horizontal alternate mode to step 4
The the first zeins liquid (quantity for spray is 30% of coating quality in step 3) for applying step 2, is subsequently placed at 45 DEG C dry
2h then uses the second zeins liquid of vertical and horizontal alternate mode spraying process 2 with the air cannon that pressure is 70psi
(quantity for spray is 50% of coating quality in step 3), continues to be placed at 45 DEG C and continues dry 4h, obtain hydrophobic automobile adhesive film.
Embodiment 2
A kind of preparation method of hydrophobic automobile adhesive film, comprising the following steps:
Step 1: ethyl orthosilicate and silane coupling agent being added into normal propyl alcohol and stirs 30min, is subsequently added into two silicon of hexamethyl
Amine alkane continues to stir 30min, deionized water is then added dropwise, then be placed under 45 DEG C of water bath conditions and be stirred to react 12h, obtains containing dioxy
The mixed liquor of SiClx nanoparticle (partial size 68.5nm), wherein the mass ratio of normal propyl alcohol, ethyl orthosilicate and silane coupling agent
It is 100: 5: 0.2, the dosage of deionized water is the 10% of normal propyl alcohol quality；
Step 2: the zeins for being equivalent to ethanol solution quality 12% being added in the ethanol solution for being 98% to volumetric concentration
And 30min is stirred, obtain the first zeins liquid；It is added in the ethanol solution for being 70% to volumetric concentration and is equivalent to ethyl alcohol
The zeins of solution quality 3% simultaneously stirs 20min, obtains the second zeins liquid；
Step 3: by the mixed liquor containing Nano particles of silicon dioxide of the step 1 of 40g, the adhesive of 20g, 5g diethanol amine,
The glycerol of the potassium peroxydisulfate of 0.8g, the stabilizer of 1.5g and 1.0g mixes, then continuous with revolving speed 800r/min using dispersion machine
Disperse 20min, standing and defoaming 60min obtains coating；
Step 4: plasma treatment is carried out to glass baseplate, the coating then prepared step 3 by spin coater be coated in it is equal from
The surface of glass baseplate after subprocessing, the glass baseplate for being then coated with coating do 3h at 60 DEG C, obtain porous gel
Film；
Step 5: spraying on the surface of porous gel film of the air cannon for being 50psi with pressure using vertical and horizontal alternate mode to step 4
The the first zeins liquid (quantity for spray is 40% of coating quality in step 3) for applying step 2, is subsequently placed at 60 DEG C dry
3h then uses the second zeins liquid of vertical and horizontal alternate mode spraying process 2 with the air cannon that pressure is 70psi
(quantity for spray is 60% of coating quality in step 3), continues to be placed at 45 DEG C and continues dry 6h, obtain hydrophobic automobile adhesive film.
Embodiment 3
A kind of preparation method of hydrophobic automobile adhesive film, comprising the following steps:
Step 1: ethyl orthosilicate and silane coupling agent being added into normal propyl alcohol and stirs 25min, is subsequently added into two silicon of hexamethyl
Amine alkane continues to stir 25min, deionized water is then added dropwise, then be placed under 40 DEG C of water bath conditions and be stirred to react 8h, obtains containing dioxy
The mixed liquor of SiClx nanoparticle (partial size 58nm), wherein the mass ratio of normal propyl alcohol, ethyl orthosilicate and silane coupling agent is
90: 4: 0.2, the dosage of deionized water is the 10% of normal propyl alcohol quality；
Step 2: the zeins for being equivalent to ethanol solution quality 11% being added in the ethanol solution for being 97% to volumetric concentration
And 25min is stirred, obtain the first zeins liquid；It is added in the ethanol solution for being 65% to volumetric concentration and is equivalent to ethyl alcohol
The zeins of solution quality 2% simultaneously stirs 15min, obtains the second zeins liquid；
Step 3: by the diethanol of the mixed liquor containing Nano particles of silicon dioxide of the step 1 of 35g, the adhesive of 20g, 3.5g
The glycerol mixing of amine, the potassium peroxydisulfate of 0.6g, the stabilizer of 1.0g and 0.75g, then using dispersion machine with revolving speed 700r/min
Continuous dispersion 18min, standing and defoaming 53min obtain coating；
Step 4: plasma treatment is carried out to glass baseplate, the coating then prepared step 3 by spin coater be coated in it is equal from
The surface of glass baseplate after subprocessing, the glass baseplate for being then coated with coating are dried 2.5h at 53 DEG C, are obtained porous
Gel mould；
Step 5: spraying on the surface of porous gel film of the air cannon for being 50psi with pressure using vertical and horizontal alternate mode to step 4
The the first zeins liquid (quantity for spray is 35% of coating quality in step 3) for applying step 2, is subsequently placed at 45 DEG C dry
2.5h then uses the second zeins liquid of vertical and horizontal alternate mode spraying process 2 with the air cannon that pressure is 70psi
(quantity for spray is 55% of coating quality in step 3), continues to be placed at 53 DEG C and continues dry 5h, obtain hydrophobic automobile adhesive film.
Comparative example 1
The comparative example with embodiment 3, the difference is that, the adhesive used is common commercial binder.
Comparative example 2
The comparative example 2 with embodiment 3, the difference is that, step 1 is changed to common commercially available Nano particles of silicon dioxide (partial size
It is distributed in normal propyl alcohol for 50 ~ 100nm) to obtain the mixed liquor containing Nano particles of silicon dioxide.
Comparative example 3
The comparative example 3 with embodiment 3, the difference is that, step 2 and step 5 are saved, directly using porous gel film as final
Automobile adhesive film.
Comparative example 4
The comparative example 3 with embodiment 3, the difference is that, in step 5, exchange the first zeins liquid and the second corn
The spraying sequence of alcohol soluble protein liquid.
Comparative example 5
The commercially available automobile adhesive film with hydrophobic effect.
Measure the film properties of each embodiment and comparative example
The evaluation that following items are carried out to the hydrophobic automobile adhesive film prepared by embodiment and comparative example, the results are shown in Table 1.
1) HR-100(Murakami Co., Japan the measurement of light transmittance: are used) evaluation light transmittance.
2) hydrophobic effect (when the static contact angle of water is greater than 150 °, it is believed that the substance has ultra-hydrophobicity)
Contact angle: using the OCA15 video optics contact angle measurement of Dataphysics company of Germany, 3 μ L of droplet size.
3) durability
Scrub performance test method: automobile adhesive film is attached on glass, is cleaned using windscreen wiper item, while applying one to windscreen wiper item
The load of a 300 g, windscreen wiper item are driven by the cylinder, and reciprocal to clean once for a circulation, scouring frequency is 48 circulations/min,
0.5% washing powder solution is added dropwise during scouring.Sample is rinsed after cleaning 60000 circulations, carries out contact angle survey after dry
It is fixed.
Table 1
| Light transmittance % | Initial contact angle/° | Clean 30000 times/° | Clean 60000 times/° | |
| Embodiment 1 | 95.6 | 156 | 151 | 147 |
| Embodiment 2 | 94.9 | 162 | 153 | 148 |
| Embodiment 3 | 96.5 | 175 | 172 | 165 |
| Comparative example 1 | 90.8 | 120 | 103 | 89 |
| Comparative example 2 | 92.5 | 101 | 93 | 88 |
| Comparative example 3 | 96.9 | 105 | 90 | 81 |
| Comparative example 4 | 88.5 | 127 | 102 | 92 |
| Comparative example 5 | 92.1 | 108 | 87 | 63 |
As shown in table 1, the present invention is mixed using adhesive prepared by the present invention, Nano particles of silicon dioxide of the invention at the same time
Liquid and the bulky grain zein liquid for first spraying high concentration stage by stage spray the reality of the little particle corn protein solution of low concentration again
It applies the resulting automobile adhesive film of 1 ~ embodiment of example 3 just while there is excellent hydrophobicity, light transmittance and durability；Bonding of the invention
Agent, Nano particles of silicon dioxide mixed liquor and by the short grained zeins liquid of low concentration after first high concentration bulky grain to changing
Hydrophobicity, light transmittance and the durability of kind automobile adhesive film play synergistic effect.
In conclusion a kind of hydrophobic automobile adhesive film provided by the invention and preparation method thereof, the present invention using it is above-mentioned containing
The adhesive that the mixed liquor of the Nano particles of silicon dioxide of hydrophobic grouping and the various of monomer similar in refraction coefficient aggregate into is simultaneously
Be aided with above-mentioned auxiliary material and construct the porous gel film with certain surface roughness, then spray two kinds of various concentrations corn alcohol it is molten
Protein liquid with formed simulation lotus leaf superhydrophobic microstructure film pattern, and then obtained high transparency and hydrophobicity it is good automobile patch
Film；The adhesive of automobile adhesive film of the invention is using ethyl acrylate, methyl acrylate and metering system similar in refraction coefficient
Acid is that monomer is polymerize, and further improves the transparency finally to form a film, further improves the light transmittance of film；The present invention adopts
Adhesive obviates the presence of double bond or phenyl ring in polymer, improves the weatherability of adhesive itself, and by dioxy
SiClx nano particle by it is fully dispersed be uniformly embedded into adhesive and other auxiliary materials and to glass baseplate carry out plasma at
The mode managed in conjunction with coating is once completed to coat, and constructs the porous gel film with certain surface roughness in advance, effectively
The binding force of film layer and substrate is improved, and can effectively prevent falling off for silicon dioxide granule, therefore also substantially increase automobile
The durability of pad pasting；The adjustment that the present invention passes through above-mentioned technique, it is ensured that the compactness of the automobile adhesive film of preparation further increases
Its transparency improves its heat-proof quality again.
The present invention is described by above-mentioned related embodiment, however above-described embodiment is only to implement example of the invention.
It must be noted that the embodiment disclosed is not limiting as the scope of the present invention.On the contrary, be included in claim spirit and
The modification of range and impartial setting are included in the scope of the present invention.
Claims (6)
1. a kind of preparation method of hydrophobic automobile adhesive film, which comprises the following steps:
Step 1: ethyl orthosilicate and silane coupling agent being added into normal propyl alcohol and stirs 20 ~ 30min, is subsequently added into hexamethyl two
Silicon amine alkane continues 20 ~ 30min of stirring, and deionized water is then added dropwise, then is placed under 35 ~ 45 DEG C of water bath conditions and is stirred to react 4 ~ 12h,
Obtain the mixed liquor containing Nano particles of silicon dioxide, wherein the mass ratio of normal propyl alcohol, ethyl orthosilicate and silane coupling agent is 80
~ 100: 3 ~ 5: 0.2, the dosage of deionized water is the 10% of normal propyl alcohol quality；
Step 2: the corn alcohol for being equivalent to ethanol solution quality 10 ~ 12% being added in the ethanol solution for being 96 ~ 98% to volumetric concentration
Molten albumen simultaneously stirs 20 ~ 30min, obtains the first zeins liquid；Add in the ethanol solution for being 60 ~ 70% to volumetric concentration
Enter to be equivalent to the zeins of ethanol solution quality 1 ~ 3% and stir 10 ~ 20min, obtains the second zeins liquid；
Step 3: by the mixed liquor containing Nano particles of silicon dioxide of the step 1 of 30 ~ 40 parts by weight, the adhesive of 20 parts by weight, 2
The diethanol amine of ~ 5 parts by weight, the potassium peroxydisulfate of 0.4 ~ 0.8 parts by weight, the stabilizer of 0.5 ~ 1.5 parts by weight and 0.5 ~ 1.0 weight
Part glycerol mixing, 15 ~ 20min is then dispersed continuously with 600 ~ 800r/min of revolving speed using dispersion machine, standing and defoaming 45 ~
60min obtains coating；
Step 4: plasma treatment is carried out to glass baseplate, the coating then prepared step 3 by spin coater be coated in it is equal from
The surface of glass baseplate after subprocessing, the glass baseplate for being then coated with coating are dried 2 ~ 3h at 45 ~ 60 DEG C, are obtained more
Hole gel mould；
Step 5: to the first zeins liquid of the surface spraying process 2 of the porous gel film of step 4, it is subsequently placed in 45 ~
Dry 2 ~ 3h at 60 DEG C, then the second zeins liquid of spraying process 2, continue to be placed at 45 ~ 60 DEG C continue dry 4 ~
6h obtains hydrophobic automobile adhesive film；
Wherein, described adhesive is grouped as by following each group by mass percentage: the ethanol solution that volumetric concentration is 70%
10%, ethyl acetate 32%, ethyl acrylate 20%, zeins 18%, methyl acrylate 12%, methacrylic acid 5%, amino
Silane coupling agent 2%, hydroxy stearic acid 0.5%, benzoyl peroxide 0.3% and lauryl mercaptan 0.2%.
2. the preparation method of hydrophobic automobile adhesive film according to claim 1, which is characterized in that the silane of the step 1 is even
It is a kind of in KH570 or KH560 for joining agent.
3. the preparation method of hydrophobic automobile adhesive film according to claim 1, which is characterized in that the first corn alcohol in step 5
The dosage of molten protein liquid is 30 ~ 40% of coating quality in step 3.
4. the preparation method of hydrophobic automobile adhesive film according to claim 1, which is characterized in that the second corn alcohol in step 5
The dosage of molten protein liquid is 50 ~ 60% of coating quality in step 3.
5. the preparation method of hydrophobic automobile adhesive film according to claim 1, which is characterized in that the concrete operations of step 5 are as follows:
With pressure be 50psi air cannon using porous gel film from vertical and horizontal alternate mode to step 4 surface spraying process 2 the
One zeins liquid is subsequently placed at 45 ~ 60 DEG C dry 2 ~ 3h, and the air cannon for being then 70psi with pressure is using vertical and horizontal
Second zeins liquid of alternate mode spraying process 2, continues to be placed at 45 ~ 60 DEG C and continues dry 4 ~ 6h, dredged
Water automobile adhesive film.
6. the hydrophobic automobile adhesive film of preparation method preparation described in a kind of any one according to claim 1 ~ 5.
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| CN115012227A (en) * | 2022-07-14 | 2022-09-06 | 江南大学 | Method for preparing hydrophobic textile by utilizing biomacromolecules |
| CN115224205A (en) * | 2022-07-22 | 2022-10-21 | 江苏旭日祥新材料科技有限公司 | Water-resistant environment-friendly photovoltaic material and preparation method thereof |
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