CN112210112A - Surface self-cleaning raw lacquer composite film and preparation method thereof - Google Patents
Surface self-cleaning raw lacquer composite film and preparation method thereof Download PDFInfo
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- CN112210112A CN112210112A CN202011118873.4A CN202011118873A CN112210112A CN 112210112 A CN112210112 A CN 112210112A CN 202011118873 A CN202011118873 A CN 202011118873A CN 112210112 A CN112210112 A CN 112210112A
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- raw lacquer
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- 239000004922 lacquer Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000004140 cleaning Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 claims abstract description 40
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 claims abstract description 40
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 claims abstract description 40
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000001020 plasma etching Methods 0.000 claims abstract description 17
- 239000003973 paint Substances 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000002202 Polyethylene glycol Substances 0.000 claims description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims description 24
- 238000005530 etching Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 33
- 239000007787 solid Substances 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
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- 239000007788 liquid Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000010329 laser etching Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 108010029541 Laccase Proteins 0.000 description 1
- 244000044283 Toxicodendron succedaneum Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002929 natural lacquer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003305 oil spill Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2393/00—Characterised by the use of natural resins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
Abstract
The invention discloses a surface self-cleaning raw lacquer composite film and a preparation method thereof, wherein the composite film is prepared by carrying out high-temperature curing film forming on urushiol and hydrophilic macromonomer and then carrying out plasma etching on the surface of the urushiol and hydrophilic macromonomer to generate a micro/nano hierarchical coarse structure. Under the synergistic effect of hydrophilic modification and a surface micro-rough structure, the surface of the raw lacquer composite film prepared by the invention presents good super-hydrophilicity, a solid/water interface is easy to replace a solid/oil interface so as to cause oil stain to be separated, and the self-cleaning of the surface of a lacquer film can be realized by a simple water cleaning method. Meanwhile, the adhesion and impact resistance of the raw lacquer composite film are remarkably improved compared with those of a natural raw lacquer film, and the raw lacquer composite film is simple in preparation process, free of complex equipment and working procedures, low in cost and suitable for large-scale production, popularization and application.
Description
Technical Field
The invention relates to a raw lacquer composite film, in particular to a raw lacquer composite film with a self-cleaning surface and a preparation method thereof.
Background
The raw lacquer is also called lacquer, natural lacquer and Chinese lacquer, and the main component of the raw lacquer is urushiol which accounts for 50-80% of the total content of the raw lacquer. The urushiol can be catalyzed by laccase in raw lacquer to be dried into a film at normal temperature or directly polymerized into a film by utilizing the side chain at high temperature due to the catechol group with the unsaturated long side chain in the structure. As the king of paint, the paint film of raw lacquer has excellent corrosion resistance, heat resistance, acid and alkali resistance and good physical and mechanical properties (adhesive force, impact resistance and the like are slightly deficient), and is applied to a plurality of fields such as petrochemical industry, navigation ships, war industry, civil furniture and the like. However, the surface of the raw lacquer film is easily polluted by oil such as industrial dirty oil, ocean oil spill and domestic oil in the application process, so that the product performance is reduced and the economic loss is serious. The common physical cleaning method has a non-ideal effect because the raw lacquer surface is hydrophobic; the chemical cleaning method has obvious effect, but has higher cost and pollutes the environment. The modification of raw lacquer to prepare the functional raw lacquer with the surface self-cleaning (easy cleaning) property is an effective way for solving the pollution of a paint film.
A superhydrophilic surface is a special wetting surface with very small contact angles with water (< 5 °) with good self-cleaning properties. When the super-hydrophilic surface is polluted by oil, the oil has small adhesion force on the surface (super-oleophobic property in water), so that when the super-hydrophilic surface is cleaned by simple water, the acting force of the water and the surface is strong, and a solid/water interface is easy to replace the solid/oil interface, thereby separating the oil stain. The preparation method of the super-hydrophilic surface is various and can be generally obtained by constructing a micro-rough structure on the surface of a hydrophilic material. The micro-roughness structure is usually formed by a simple etching method, such as a chemical etching method, a laser etching method, etc. The chemical etching method is simple and convenient to operate, but is easy to damage the mechanical property of the matrix and can generate chemical pollution; the laser etching method has high stability, but has high equipment cost and low etching rate, and cannot meet the requirement of mass production.
Disclosure of Invention
The invention aims to provide a raw lacquer composite film with good self-cleaning performance due to super-hydrophilic surface and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a surface self-cleaning raw lacquer composite film is prepared by high-temperature curing urushiol and hydrophilic macromonomer to form a film, and then carrying out plasma etching on the surface of the film.
The hydrophilic macromonomer comprises any one of polyethylene glycol diacrylate (CAS: 26570-48-9), polyethylene glycol dimethacrylate (CAS: 25852-47-5), polyethylene glycol methyl ether methacrylate (CAS: 26915-72-0) and methoxy polyethylene glycol acrylate (CAS: 32171-39-4).
The preparation method of the surface self-cleaning raw lacquer composite film comprises the following steps:
the method comprises the following steps: extracting urushiol from raw lacquer by an ethanol method;
step two: dissolving urushiol and a hydrophilic macromonomer in a solvent according to a mass percent ratio of (90:10) - (70:30) to form a mixed solution, and controlling the total mass concentration of the urushiol and the hydrophilic macromonomer in the mixed solution to be 60-80%; the solvent is xylene or toluene;
step three: coating the mixed solution, heating at 100-140 ℃ for 4-12 h, and drying to form a film;
step four: carrying out plasma surface etching treatment on the paint film obtained in the step three to obtain the surface self-cleaning raw paint composite film; in the plasma etching treatment, the etching gas is any one of argon, oxygen or nitrogen, the etching pressure is 5-30 Pa, the etching power is 50-100W, and the etching time is 0.5-3 min.
The thickness of the obtained composite film is 50 to 200 μm, preferably 100 μm.
According to the invention, hydrophilic macromonomer and urushiol are introduced to be copolymerized into a film at a high temperature, and then the surface of the obtained paint film is subjected to plasma etching to generate a micro/nano hierarchical coarse structure. Under the synergistic effect of hydrophilic modification and a surface micro-rough structure, the surface of the raw lacquer composite membrane presents good super-hydrophilicity, a solid/water interface is easy to replace a solid/oil interface so as to cause oil stain to be separated, and the self-cleaning of the surface of a lacquer film can be realized by a simple water cleaning method. In addition, the polyethylene glycol acrylate hydrophilic macromonomer contains carbon-carbon double bonds, and can generate copolymerization reaction with unsaturated long side chains in urushiol, and the curing film forming speed of the polyethylene glycol acrylate hydrophilic macromonomer and the unsaturated long side chains in urushiol is high. Meanwhile, a polyethylene glycol chain segment is introduced into the raw lacquer composite film structure, and the adhesion of a lacquer film can be improved due to high polarity and strong acting force with a substrate; and because of large flexibility and good toughness, the rigidity of a benzene ring structure in a natural raw paint film can be overcome, so that the impact resistance of the paint film can be improved. In addition, compared with a chemical etching method and a laser etching method, the technical scheme adopts plasma etching, the etching area only relates to the shallow surface of the material, the substrate performance of the material is not influenced, the method is efficient and environment-friendly, and the requirement on equipment is not high.
Compared with the prior art, the invention has the following remarkable effects:
(1) according to the invention, through copolymerization modification of urushiol and hydrophilic macromonomer, the hydrophilicity of the surface of a raw paint film is improved, a micro/nano hierarchical coarse structure is further constructed on the surface of the paint film through plasma etching, the hydrophilicity of the surface of the paint film is greatly enhanced, and the contact angle between the surface of the paint film and water can be reduced to below 5 ℃;
(2) the raw lacquer composite membrane prepared by the invention is cleaned by simple water after the surface is pre-polluted, and the residual oil quantity on the surface is only 0.1 percent. Due to good super-hydrophilicity of the surface of the paint film, the paint film has super-oleophobic property in water, the oil contact angle can reach 168.8-172.3 degrees, and the oil adhesion work and the adhesion force can be respectively reduced to 0.5-1.0 mJ/m2And 1 μ N, the solid/oil interface is easily replaced by a solid/water interface to detach the oil stain;
(3) the raw lacquer composite film prepared by the method effectively improves partial physical and mechanical properties of a natural raw lacquer film, the adhesive force of the composite film can reach 1 grade or 0 grade, the impact resistance can reach 90-100 cm, and the impact resistance is obviously higher than that of the natural raw lacquer film;
(4) the preparation method is simple in preparation process, low in cost and suitable for large-scale production, popularization and application, and does not need complex equipment and procedures.
Drawings
FIG. 1 is a comparison graph of the IR spectra of paint films prepared in example 1 and comparative example 3;
FIG. 2 is a SEM comparison of the surfaces of paint films prepared in example 1 and comparative example 3.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Adding 75mL of absolute ethyl alcohol into 25g of raw lacquer liquid, fully stirring, standing for layering, pouring out supernatant, and removing ethanol and residual water in clear liquid by using a reduced pressure distillation method to obtain urushiol with the purity of more than 95%;
taking 6g of dimethylbenzene, respectively adding 9.8g of urushiol and 4.2g of polyethylene glycol methyl ether methacrylate with the molecular weight of 475, fully stirring to fully dissolve the urushiol and the polyethylene glycol methyl ether methacrylate, uniformly coating the solution on a clean glass sheet or a tinplate polished by abrasive paper by using a four-side preparation device, heating for 8 hours in an oven to cure to form a film, and then carrying out plasma etching on the surface of the paint film for 1.5 minutes under the conditions of argon atmosphere, pressure of 15Pa and power of 75W to prepare the surface self-cleaning raw paint composite film with the thickness of 100 mu m.
Example 2
Adding 105mL of absolute ethyl alcohol into 35g of raw lacquer liquid, fully stirring, standing for layering, pouring out supernatant, and removing ethanol and residual water in clear liquid by using a reduced pressure distillation method to obtain urushiol with the purity of more than 95%;
taking 4g of toluene, respectively adding 14.4g of urushiol and 1.6g of polyethylene glycol diacrylate with the molecular weight of 600, fully stirring to fully dissolve the urushiol and the polyethylene glycol diacrylate, uniformly coating the solution on a clean glass sheet or a tin sheet polished by sand paper by using a four-side preparation device, heating the solution in an oven for 12 hours to solidify and form a film, and then carrying out plasma etching on the surface of the paint film for 0.5min under the conditions of nitrogen atmosphere, the pressure of 30Pa and the power of 100W to prepare the surface self-cleaning raw lacquer composite film with the thickness of 50 mu m.
Example 3
Adding 75mL of absolute ethyl alcohol into 25g of raw lacquer liquid, fully stirring, standing for layering, pouring out supernatant, and removing ethanol and residual water in clear liquid by using a reduced pressure distillation method to obtain urushiol with the purity of more than 95%;
taking 8g of dimethylbenzene, respectively adding 10.2g of urushiol and 1.8g of methoxypolyethylene glycol acrylate with the molecular weight of 480, fully stirring to fully dissolve the urushiol and the methoxypolyethylene glycol acrylate, uniformly coating the solution on a clean glass sheet or a tin sheet polished by sand paper by using a four-side preparation device, heating the solution in an oven for 4 hours to solidify and form a film, and then carrying out plasma etching on the surface of the paint film for 3 minutes under the conditions of oxygen atmosphere, the pressure of 5Pa and the power of 50W to prepare the surface self-cleaning raw lacquer composite film with the thickness of 200 mu m.
Comparative example 1
Adding 75mL of absolute ethyl alcohol into 25g of raw lacquer liquid, fully stirring, standing for layering, pouring out supernatant, and removing ethanol and residual water in clear liquid by using a reduced pressure distillation method to obtain urushiol with the purity of more than 95%; and then uniformly coating the obtained urushiol on a clean glass sheet or a tinplate sheet polished by sand paper by using a four-side preparation device, and heating the mixture in an oven at 120 ℃ for 6 hours to solidify and form a film so as to obtain a natural raw paint film.
Comparative example 2
Adding 75mL of absolute ethyl alcohol into 25g of raw lacquer liquid, fully stirring, standing for layering, pouring out supernatant, and removing ethanol and residual water in clear liquid by using a reduced pressure distillation method to obtain urushiol with the purity of more than 95%; and then uniformly coating the obtained urushiol on a clean glass sheet by using a four-side preparation device, heating the urushiol in an oven at 120 ℃ for 6 hours to solidify and form a film, and then carrying out plasma etching on the surface of the paint film for 1.5min under the conditions of argon atmosphere, pressure of 15Pa and power of 75W to obtain the natural raw paint film with the etched surface.
Comparative example 3
Adding 75mL of absolute ethyl alcohol into 25g of raw lacquer liquid, fully stirring, standing for layering, pouring out supernatant, and removing ethanol and residual water in clear liquid by using a reduced pressure distillation method to obtain urushiol with the purity of more than 95%; and then taking 6g of dimethylbenzene, respectively adding 9.8g of urushiol and 4.2g of polyethylene glycol methyl ether methacrylate with the molecular weight of 475, fully stirring to fully dissolve the urushiol and the polyethylene glycol methyl ether methacrylate, uniformly coating the solution on a clean glass sheet by using a four-side preparation device, and heating the glass sheet in an oven at 120 ℃ for 8 hours to solidify and form a film, so as to obtain the hydrophilic modified natural raw paint film.
FIG. 1 is a comparison of the IR spectra of the paint films prepared in example 1 and comparative example 3. As shown in FIG. 1, the concentration of urushiol and polyethylene glycol methyl ether methacrylate in 1590-1620 cm after curing to form a film (comparative example 3)-1In the range of 3388cm-1The vibration absorption peak and the O-H stretching vibration peak of the benzene ring skeleton of the urushiol are respectively shown at the positions of 1723cm-1And 1093cm-1The stretching vibration peaks of C = O and C-O-C of poly (methoxy polyethylene glycol methacrylate) respectively appear at the positions, which shows that the urushiol and the methoxy polyethylene glycol methacrylate can generate copolymerization reaction to form a film after being heated. After plasma etching, the infrared spectrum of the paint film (example 1) has not changed significantly, which indicates that the plasma etching effect does not affect the chemical structure of the paint film.
FIG. 2 is a SEM comparison of the surfaces of paint films prepared in example 1 and comparative example 3. As can be seen from FIG. 2, the surface of urushiol and polyethylene glycol methyl ether methacrylate is smooth and has low roughness after copolymerization to form a film (comparative example 3). After plasma etching, the microscopic morphology of the surface of the paint film (example 1) is changed remarkably, spherical particles with the size of several micrometers (about 1 μm) are uniformly generated, and a large number of small spherical particles with the size of nanometer (about 100-300 nm) are gathered near the surface of the paint film, so that the roughness of the surface of the paint film is greatly increased due to the generation of the micro/nano particles.
Performance testing
The related performance test method is as follows:
contact angle test: the contact angle of the paint film surface was measured with a DSA-100 contact Angle measuring apparatus from Kruss, Germany, the water contact angle test was conducted in air, the oil (hexadecane) contact angle test was conducted in water, the volumes of the water drop and the oil drop (hexadecane) were 2. mu.L each, and the measurements were averaged for 5 times.
And (3) calculating the adhesion work: the work of adhesion of oil droplets on the surface of the paint film was calculated according to the following formula (a)W a：
In the formula, gammaowIs free energy at oil/water interface, and has a value of 53.3mJ/m2（25℃），θThe contact angle of oil in water.
And (3) adhesion testing: the paint film surface was tested for adhesion using a BSA124S microbalance system. The paint film is placed at the bottom of a transparent glass box filled with water, and the glass box is flatly placed on a scale pan of a balance. In the test, oil droplets suspended and fixed on a metal O-ring (hexadecane, 2. mu.L) were moved down to contact the paint film surface, and then slowly moved up at a speed of 0.01mm/s until they were pulled off the paint film surface. The force change during the oil drop pull-off was continuously recorded by the balance-configured software, where the maximum force at the moment the oil drop left the sample surface was defined as the adhesion force. The average was taken 5 times of the test.
Self-cleaning performance evaluation: and evaluating the easy-cleaning performance of the paint film surface by using hexadecane as a model oil pollutant and adopting a simple water cleaning method. Pre-polluting the surface of the paint film with metered oil drops, then simply cleaning with water, drying the paint film in vacuum at room temperature after cleaning, weighing, and obtaining the residual oil on the surfaceO RCalculated as follows:
in the formula (I), the compound is shown in the specification,W 0in order to contaminate the weight of the oil droplets,W 1in order to be the weight of the paint film uncontaminated,W 2is the weight of the polluted paint film after being cleaned.
Adhesion and impact resistance testing: the adhesion and impact resistance of the paint films were tested using GB/T1720-79 and GB/T1732-1993, respectively.
The paint films prepared in examples 1-3 and comparative examples 1-3 were subjected to contact angle test, adhesion work calculation, adhesion test and self-cleaning performance evaluation, the paint film coated on the glass sheet was selected during the test, and the test results are shown in table 1.
TABLE 1 contact angle, work of adhesion, adhesion and cleaning effect of paint film surface
As can be seen from Table 1, the surface of the natural raw paint film (comparative example 1) has low hydrophilicity, and after the natural raw paint film is subjected to plasma etching (comparative example 2) or subjected to copolymerization film formation by introducing hydrophilic macromonomers (comparative example 3), the surface hydrophilicity is improved to a certain extent, the oil repellency in water is improved, the oil adhesion work and the adhesion force are reduced, but more oil stain residues (16.8-20.4%) are remained after the surface is polluted and water washing. The raw lacquer composite film (examples 1-3) obtained by copolymerizing urushiol and hydrophilic macromonomer to form a film and performing plasma etching on the film has a surface water contact angle of less than 5 degrees and good super-hydrophilicity, so that the water oil contact angle in water can be as high as 168.8-172.3 degrees, and the oil adhesion work and the adhesion force can be respectively as low as 0.5-1.0 mJ/m2And 1 μ N. At the moment, the oil is extremely small in adhesion with the surface of the composite membrane, the acting force of water on the surface of the composite membrane is strong, the solid/oil interface is easily replaced by the solid/water interface so as to promote oil stain to be separated, the residual oil amount on the surface of the composite membrane is only 0.1%, and the self-cleaning performance is excellent.
It is clear that the self-cleaning properties of the raw lacquer composite film are due to the super-hydrophilicity presented on the surface thereof, which is generated under the synergistic effect of both the hydrophilic modification of the lacquer film and the micro-roughness structure of the surface. The hydrophilicity (but not super hydrophilicity) of the natural raw lacquer film can be improved by introducing hydrophilic macromonomer to copolymerize with urushiol. Further, the micro/nano graded rough structure generated on the surface of the hydrophilic modified paint film (figure 2) can greatly enhance the hydrophilicity of the surface of the hydrophilic modified paint film, and finally the surface of the raw lacquer composite film has super-hydrophilicity.
The paint films prepared in examples 1-3 and comparative example 1 were subjected to adhesion and impact resistance tests, wherein the paint film coated on the tinplate sheet was selected during the test, and the test results are shown in table 2.
TABLE 2 adhesion and impact resistance of the paint films
As can be seen from Table 2, the adhesion force of the raw lacquer composite films (examples 1-3) can reach grade 1 or 0, the impact resistance can reach 90-100 cm, and the impact resistance is obviously higher than that of a natural raw lacquer film (comparative example 1), so that the natural raw lacquer film can effectively improve part of physical and mechanical properties of the natural raw lacquer film. The polyethylene glycol chain segment is introduced into the raw lacquer composite film structure, so that the polyethylene glycol has high polarity and strong acting force with a substrate, and the adhesive force of a paint film can be improved; and the polyethylene glycol has good flexibility, and can overcome the rigidity of a benzene ring structure in a natural raw paint film, so that the impact resistance of the paint film can be improved.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A preparation method of a surface self-cleaning raw lacquer composite film is characterized by comprising the following steps: the composite film is prepared by carrying out plasma etching on the surface of urushiol and hydrophilic macromonomer after high-temperature curing and film forming.
2. The method for preparing the surface self-cleaning raw lacquer composite film according to claim 1, comprising the following steps:
the method comprises the following steps: extracting urushiol from raw lacquer by an ethanol method;
step two: dissolving urushiol and hydrophilic macromonomer in a solvent to form a mixed solution;
step three: coating the mixed solution, heating at 100-140 ℃ for 4-12 h, and drying to form a film;
step four: and (4) carrying out plasma surface etching treatment on the paint film obtained in the step three to obtain the surface self-cleaning raw lacquer composite film.
3. The method for preparing the surface self-cleaning raw lacquer composite film according to claim 1 or 2, characterized in that: the hydrophilic macromonomer comprises any one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol methyl ether methacrylate and methoxy polyethylene glycol acrylate.
4. The method for preparing the surface self-cleaning raw lacquer composite film according to claim 2, wherein the method comprises the following steps: the mass percentage ratio of the urushiol to the hydrophilic macromonomer used in the second step is (90:10) - (70:30), and the total mass concentration of the urushiol and the hydrophilic macromonomer in the mixed solution is 60-80%; the solvent used is xylene or toluene.
5. The method for preparing the surface self-cleaning raw lacquer composite film according to claim 2, wherein the method comprises the following steps: in the plasma etching treatment, the etching gas is any one of argon, oxygen or nitrogen, the etching pressure is 5-30 Pa, the etching power is 50-100W, and the etching time is 0.5-3 min.
6. A surface self-cleaning raw lacquer composite film prepared by the method of any one of claims 1 to 5, characterized in that: the thickness of the composite film is 50-200 mu m.
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