CN113861481B - High-transmittance hydrophobic optical polyimide composite film material and preparation method thereof - Google Patents
High-transmittance hydrophobic optical polyimide composite film material and preparation method thereof Download PDFInfo
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- CN113861481B CN113861481B CN202111119728.2A CN202111119728A CN113861481B CN 113861481 B CN113861481 B CN 113861481B CN 202111119728 A CN202111119728 A CN 202111119728A CN 113861481 B CN113861481 B CN 113861481B
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229920001721 polyimide Polymers 0.000 title claims abstract description 53
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000004642 Polyimide Substances 0.000 title claims abstract description 28
- 238000002834 transmittance Methods 0.000 title claims abstract description 24
- 230000003287 optical effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 239000003292 glue Substances 0.000 claims description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 229920005575 poly(amic acid) Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000003880 polar aprotic solvent Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 5
- 150000004984 aromatic diamines Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000003847 radiation curing Methods 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000001723 curing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 230000005661 hydrophobic surface Effects 0.000 abstract description 2
- 238000012634 optical imaging Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 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
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- 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
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08J5/18—Manufacture of films or sheets
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a high-transmittance hydrophobic optical polyimide composite film material and a preparation method thereof. The invention obtains the optical flexible polyimide composite film material with high transmittance in a visible light region and hydrophobic surface. The composite film has great application prospect in the fields of screen display, optical imaging, solar cells, high-energy laser systems, aerospace and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a high-transmittance hydrophobic optical polyimide composite film material and a preparation method thereof.
Background
The polyimide film material has the advantages of light surface density, good thermal stability, high strength, resistance to electrical resistance, excellent chemical corrosion resistance, mild synthesis and forming process, large modification space and the like, and is widely applied to the fields of aerospace, electronic industry, screen display and the like.
However, charge Transfer Complexation (CTC) exists between molecules of the aromatic polyimide material, and is caused by charge transfer or charge polarization generated when electricity-rich and electricity-deficient groups generated by the repeated dianhydride and diamine structural units on a molecular chain approach, and the interaction has obvious influence on the optical performance of the material. Macroscopically, the film material has low transmittance in the visible light region, so that the further application of the film material in the optical field is limited.
Although the traditional polyimide material has excellent performance, groups with stronger hydrophilicity, such as carbonyl (capable of forming hydrogen bond with water) and imide ring (strong polar substance), exist in a molecular chain. Meanwhile, due to the fact that the difference of molecular chain aggregation states can cause physical adsorption of free water, polyimide has a strong moisture absorption characteristic. After moisture absorption, a slight residual stress is formed in the material. For optical application grade polyimide film materials, the deformation of the optical polyimide film can be brought by the tiny residual stress, and the creep of the material can be caused under the action of long-term stress, so that the long-term engineering application is not facilitated.
The silicon dioxide antireflection film is widely applied to antireflection of lenses made of inorganic substrate materials such as quartz glass lenses, and the silicon dioxide antireflection film is an optical material widely applied due to the fact that the preparation method is relatively simple, and the silicon dioxide antireflection film has excellent heat resistance, lower refractive index, low dielectric property, higher chemical stability, good mechanical strength and the like.
The surface of the material can be subjected to hydrophobic modification through surface material group modification, and the Octadecyl Trichlorosilane (OTS) is an excellent hydrophobic agent and can react with the surface of the film layer to reduce the free energy of the surface of the film so as to achieve the hydrophobic effect.
Disclosure of Invention
Aiming at the problems of low visible light region transmittance and strong water absorption of the existing polyimide film, the invention provides a high-transmittance hydrophobic optical polyimide composite film material and a preparation method thereof. Namely, one of the purposes of the invention is to provide a polyimide composite film material with high-transparency and hydrophobic surface; the second purpose of the invention is to provide a preparation method of the polyimide composite film material with the high-transmittance surface hydrophobic, the transmittance of the prepared polyimide composite film material at 560nm is 94.06%, which is improved by 15.05% compared with the transmittance of 79.01% of a pure polyimide film (25 μm) without a silicon dioxide anti-reflection hydrophobic film, the average transmittance of the composite film material in the visible light wavelength range of 500-800 nm is 93.5%, and the average transmittance of 81.5% of the pure polyimide film without a silicon dioxide anti-reflection hydrophobic film is improved by 12%. The water contact angles of the upper surface and the lower surface of the composite film after coating treatment are 123.5 degrees, and the composite film shows better hydrophobic property compared with a pure polyimide film which is not coated with a silicon dioxide antireflection hydrophobic film and has 71.7 degrees.
In order to achieve the above object, the present invention provides the following solutions:
a high-transmittance hydrophobic optical polyimide composite film material is prepared by firstly mixing aromatic diamine and aromatic dianhydride monomers in a molar ratio of 1: (0.98-1.01), performing polycondensation reaction, performing spin coating on the formed polyamic acid glue solution to form a film, performing thermal imidization to obtain a polyimide film, then dipping the film into silicon dioxide sol by a pulling method, performing ultraviolet irradiation curing to obtain silicon dioxide films on the upper surface and the lower surface of the polyimide film, and performing surface hydrophobic treatment to obtain the polyimide film.
The silicon dioxide sol is prepared by mixing Tetraethoxysilane (TEOS), hexamethyldisilazane (HMDS) and an organic solvent as a precursor, aging for several days at normal temperature, adding a photoinitiator and stirring. The pulling speed of the pulling method is 2 cm/min-8 cm/min. The ultraviolet radiation curing method adopts an 800W high-pressure mercury lamp as an ultraviolet light source; the surface hydrophobic treatment adopts Octadecyl Trichlorosilane (OTS) for hydrophobic treatment.
Furthermore, the thickness of the polyimide film in the composite film is 18-30 μm, and the thicknesses of the anti-reflection hydrophobic silicon dioxide films on the upper surface and the lower surface are both 60-200 nm. Preferably, the thickness of the polyimide film in the composite film is 25 μm, and the thicknesses of the anti-reflection hydrophobic silicon dioxide films on the upper surface and the lower surface are both 100nm.
In the invention, the reaction of the polyamic acid glue solution needs to be carried out at the reaction temperature of 0-25 ℃ for 24-48 hours.
In the invention, the aromatic dianhydride is one or a mixture of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) or pyromellitic dianhydride (PMDA);
in the invention, the aromatic diamine is one or a mixture of more of 4,4 '-Diaminobenzanilide (DABA) and 4,4' -diaminodiphenyl ether (ODA);
in the invention, the preparation method of the polyimide double-surface silicon dioxide antireflection film is a silicon dioxide sol pulling method and is obtained by ultraviolet curing.
The surface hydrophobicity of the composite film is obtained by performing surface treatment on the composite film by using Octadecyltrichlorosilane (OTS).
The invention also aims to provide a preparation method of the high-transmittance hydrophobic optical polyimide composite film material, which comprises the following steps:
(1) under the protection of nitrogen, dispersing diamine monomer in a polar aprotic solvent, stirring and dissolving, adding dianhydride monomer in batches, wherein the molar ratio of the diamine monomer to the dianhydride monomer is 1: (0.98-1.01), stirring the mixed solution at 0-25 ℃ for 24-48 hours, adding an end-capping reagent after the reaction is finished to control the molecular weight of the glue solution to be 10000-15000 cp (dynamic viscosity), and obtaining the polyamic acid composite glue solution, wherein the solid content of the polyamic acid composite glue solution is 10-15 wt%. Preferably, removing bubbles of the glue solution in vacuum, coating the polyamic acid composite glue solution on a substrate in a rotating manner to form a film, prebaking at 75-80 ℃, then performing thermal imidization by programmed heating (100 ℃,200 ℃,300 ℃,400 ℃), and removing the substrate after the thermal imidization is completed to obtain the polyimide optical film material;
(2) mixing Tetraethoxysilane (TEOS), hexamethyldisilazane (HMDS) and an organic solvent according to a mass ratio of 1-1.5 to 0.1-0.3. The double-sided ultraviolet radiation curing is carried out under a high-pressure mercury lamp. For example, the high-pressure mercury lamp is an 800W high-pressure mercury lamp.
(3) And (3) soaking the cured composite film into an Octadecyl Trichlorosilane (OTS)/toluene solution, reacting for 1-2 hours, and naturally airing in the filtered air after the reaction is finished to finish surface hydrophobic treatment. Wherein, the Octadecyl Trichlorosilane (OTS)/toluene solution is formed by dissolving Octadecyl Trichlorosilane (OTS) in toluene.
The polar aprotic solvent in the invention is N-methylpyrrolidone solvent or acetone.
The organic solvent in the invention is ethanol.
The end-capping agent is isophthalic acid.
The invention has the effective effects that: the transmittance of the prepared polyimide composite film material at 560nm is 94.06%, which is improved by 15.05% compared with the transmittance (79.01%) of a pure polyimide film (25 μm) without a silicon dioxide antireflection hydrophobic film, the average transmittance of the composite film material in the visible light wavelength range of 500-800 nm is 93.5%, and the average transmittance of the composite film material in the visible light wavelength range is improved by 12% compared with the average transmittance (81.5%) of the pure polyimide film without a silicon dioxide antireflection hydrophobic film. The water contact angle of the upper surface and the lower surface of the composite film after coating treatment is 123.5 degrees, and the composite film shows better hydrophobic property compared with a pure polyimide film which is not coated with the silicon dioxide anti-reflection hydrophobic film and has 71.7 degrees. The composite film can be widely applied to the fields of screen display, optical imaging, solar cells, high-energy laser systems, aerospace and the like.
Drawings
In order to make the purpose, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings:
FIG. 1 is a graph showing the transmittance of the polyimide composite film after the double-sided coating and hydrophobic treatment in example 1 compared with that of the uncoated polyimide film.
FIG. 2 shows the results of the water contact angle test of the polyimide composite film after the double-sided coating and hydrophobic treatment and the uncoated polyimide film in example 1.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The test methods in the examples, in which the specific conditions are not specified, are generally carried out under the conventional conditions or under the conditions recommended by the manufacturers.
Example 1
(1) Introducing nitrogen into a 50ml three-neck round bottom flask equipped with a stirrer, firstly dispersing 0.0050mol of DABA in a polar aprotic solvent acetone, stirring and dissolving, adding 0.0050mol of BPDA in batches, continuously stirring the mixed solution at room temperature for reaction for 30 hours, adding an end-capping agent isophthalic acid after the reaction is finished to control the molecular weight of a glue solution to be 10000-15000 cp (dynamic viscosity), obtaining a polyamic acid composite glue solution with the solid content (polyimide) of 15wt%, removing bubbles of the obtained glue solution in vacuum, spinning a wet film of the polyamic acid composite glue solution with a certain thickness on a quartz substrate by using a spinning machine, pre-drying the wet film of the glue solution by a heating plate (80 ℃ and 1 hour), then carrying out thermal imidization by programmed heating (100 ℃ for 1 hour, 200 ℃ for 1 hour, 300 ℃ for 1 hour and 400 ℃ for 1 hour), and carrying out film removal after the thermal imidization process is finished to obtain a uniform film with the thickness of about 25 mu m.
(2) Mixing Tetraethoxysilane (TEOS), hexamethyldisilazane (HMDS) and an organic solvent ethanol according to a mass ratio of 1:0.2 to obtain a mixed solution, aging the mixed solution as a precursor at normal temperature for 3 days, adding 20wt% (based on the total weight of Tetraethoxysilane (TEOS), hexamethyldisilazane (HMDS), an organic solvent ethanol and a photoinitiator diphenyl (2, 4,6 '-trimethylbenzoyl) phosphine oxide) of photoinitiator diphenyl (2, 4,6' -trimethylbenzoyl) phosphine oxide, stirring under the protection of nitrogen to obtain silica sol, soaking the polyimide film prepared in the previous step into the silica sol, performing double-sided coating on the polyimide film by using the silica sol by using a pulling method at a pulling speed of 5cm/min, and finally performing double-sided ultraviolet radiation curing on the composite film at a high pressure of 800W for 30min to obtain the cured composite film. The thickness of the silicon dioxide film on the upper surface is about 100nm, and the thickness of the silicon dioxide film on the lower surface is about 100nm.
(3) And finally, dipping the cured composite film into an Octadecyl Trichlorosilane (OTS)/toluene (formed by dissolving Octadecyl Trichlorosilane (OTS) in toluene, wherein the concentration of the octadecyl trichlorosilane is 5 mmol/L) solution, reacting for 1 hour, and naturally airing in filtered air after the reaction is finished to finish surface hydrophobic treatment. The transmittance of the obtained composite film was compared with that of an uncoated polyimide film (transmittance tester: model Lambda 1050, manufactured by Perkin Elmer) as shown in FIG. 1, and the surface water contact angle (surface water contact angle tester: model OCA14, manufactured by Dataphysics) as shown in FIG. 2. As shown in FIG. 2, the water contact angle of the surface of the composite film prepared in example 1 of the present invention is 123.5 degrees, and the water contact angle of the surface of the uncoated polyimide pure film is 71.7 degrees.
Example 2
(1) Introducing nitrogen into a 50ml three-neck round bottom flask equipped with a stirrer, firstly dispersing 0.0050mol of dianhydride monomer DABA and ODA (DABA: ODA molar ratio = 1) in polar aprotic solvent acetone, stirring and dissolving, adding 0.0050mol of BPDA in batches, continuously stirring the mixed solution at room temperature for reaction for 24 hours, adding end-capping agent isophthalic acid after the reaction is finished to control the molecular weight of the glue solution to be 10000-15000 cp, obtaining a polyamic acid composite glue solution with the solid content (polyimide) of 15wt%, carrying out vacuum defoaming on the obtained glue solution, carrying out spin coating on a quartz substrate by using a spin coater to form a polyamic acid composite glue solution wet film with a certain thickness, carrying out pre-drying (80 ℃ and 1 hour) treatment by a heating plate, carrying out temperature programming (100 ℃ and 1 hour), carrying out thermal imidization (200 ℃ and 300 ℃ and 400 ℃ and 1 hour), and carrying out film stripping after the thermal imidization process is finished to obtain a uniform film with the thickness of about 25 mu m.
(2) Mixing Tetraethoxysilane (TEOS), hexamethyldisilazane (HMDS) and an organic solvent ethanol according to a mass ratio of 1.
(3) And finally, dipping the cured composite film into an Octadecyl Trichlorosilane (OTS)/toluene solution (formed by dissolving Octadecyl Trichlorosilane (OTS) in toluene, wherein the concentration of the octadecyl trichlorosilane is 5 mmol/L), reacting for 1 hour, and naturally airing in filtered air after the reaction is finished to finish surface hydrophobic treatment.
Example 3
(1) Introducing nitrogen into a 50ml three-neck round bottom flask equipped with a stirrer, firstly dispersing 0.0050mol of dianhydride monomer DABA and ODA (DABA: ODA molar ratio = 1) in polar aprotic solvent acetone, stirring and dissolving, adding 0.0050mol of diamine monomer BPDA and PMDA (DABA: ODA molar ratio = 1.
(2) Mixing Tetraethoxysilane (TEOS), hexamethyldisilazane (HMDS) and organic solvent ethanol according to a mass ratio of 1: 0.2.
(3) And finally, dipping the cured composite film into an Octadecyl Trichlorosilane (OTS)/toluene solution (formed by dissolving Octadecyl Trichlorosilane (OTS) in toluene, wherein the concentration of the Octadecyl Trichlorosilane (OTS) is 5 mmol/L), reacting for 1 hour, and naturally airing in filtered air after the reaction is finished to finish surface hydrophobic treatment.
Example 4
(1) Introducing nitrogen into a 50ml three-neck round bottom flask provided with a stirrer, firstly dispersing 0.0049mol of ODA in a polar aprotic solvent acetone, stirring and dissolving, adding 0.0050mol of PMDA in batches, continuously stirring the mixed solution at room temperature for reaction for 24 hours, adding an end capping agent isophthalic acid after the reaction is finished to control the molecular weight of a glue solution to be 10000-15000 cp, obtaining a polyamic acid composite glue solution with the solid content (polyimide) of 15wt%, removing bubbles of the obtained glue solution in vacuum, spinning a wet film of the polyamic acid composite glue solution with a certain thickness on a quartz substrate by using a spinning machine, pre-drying the wet film by a heating plate (80 ℃,1 hour), then carrying out thermal imidization by programming temperature rise (100 ℃ for 1 hour, 200 ℃ for 1 hour, 300 ℃ for 1 hour and 400 ℃ for 1 hour), and carrying out film removal after the thermal imidization process to obtain a uniform film with the thickness of about 25 mu m.
(2) Mixing Tetraethoxysilane (TEOS), hexamethyldisilazane (HMDS) and an organic solvent ethanol according to a mass ratio of 1.
(3) And finally, dipping the cured composite film into an Octadecyl Trichlorosilane (OTS)/toluene solution (formed by dissolving Octadecyl Trichlorosilane (OTS) in toluene, wherein the concentration of the Octadecyl Trichlorosilane (OTS) is 5 mmol/L), reacting for 1 hour, and naturally airing in filtered air after the reaction is finished to finish surface hydrophobic treatment.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (4)
1. A preparation method of a high-transmittance hydrophobic optical polyimide composite film material is characterized by comprising the following steps: the polyimide composite film material is prepared by mixing aromatic diamine and aromatic dianhydride monomer in a molar ratio of 1: (0.98-1.01), performing polycondensation reaction, performing spin coating on the formed polyamic acid glue solution to form a film, performing thermal imidization to obtain a polyimide film, then dipping the film in silica sol by a pulling method, performing ultraviolet irradiation curing to obtain silica films on the upper surface and the lower surface of the polyimide film, and performing surface hydrophobic treatment to obtain the polyimide film;
the aromatic dianhydride is one or a mixture of 3,3', 4' -biphenyl tetracarboxylic dianhydride or pyromellitic dianhydride; the aromatic diamine is one or a mixture of 4,4 '-diaminobenzanilide or 4,4' -diaminodiphenyl ether; the silicon dioxide sol is prepared by mixing tetraethoxysilane, hexamethyldisilazane and a solvent to be used as a precursor, aging the precursor for several days at normal temperature, and adding a photoinitiator for stirring;
the pulling speed of the pulling method is 2 cm/min-8 cm/min; the ultraviolet radiation curing method adopts a high-pressure mercury lamp as an ultraviolet light source; the surface hydrophobic treatment adopts octadecyl trichlorosilane for hydrophobic treatment; the thickness of the polyimide film in the composite film is 18-30 mu m, the thickness of the anti-reflection hydrophobic silicon dioxide film on the upper surface is 60-200 nm, and the thickness of the anti-reflection hydrophobic silicon dioxide film on the lower surface is 60-200 nm;
the preparation method comprises the following steps:
(1) under the protection of nitrogen, dispersing diamine monomer in a polar aprotic solvent, stirring and dissolving, adding dianhydride monomer in batches, wherein the molar ratio of the diamine monomer to the dianhydride monomer is 1: (0.98-1.01), stirring the mixed solution at 0-25 ℃ for 24-48 hours, adding a terminating agent after the reaction is finished to control the molecular weight of the glue solution to be 10000-15000 cp, and obtaining the polyamic acid composite glue solution, wherein the solid content of the polyamic acid composite glue solution is 10-15 wt%; removing bubbles of the glue solution in vacuum, namely, spinning the polyamic acid composite glue solution on a substrate to form a film, pre-drying at 75-80 ℃, performing temperature programming thermal imidization, and removing the substrate after the thermal imidization is completed to obtain a polyimide film;
(2) mixing tetraethoxysilane, hexamethyldisilazane and an organic solvent according to a mass ratio of 1-1.5;
(3) and (3) soaking the cured composite film into an octadecyl trichlorosilane/toluene solution, reacting for 1-2 hours, and naturally airing in filtered air after the reaction is finished to finish surface hydrophobic treatment.
2. The method for preparing the polyimide composite film material according to claim 1, wherein the polar aprotic solvent is an N-methylpyrrolidone solvent or acetone.
3. The method for preparing the polyimide composite film material according to claim 1, wherein the organic solvent is ethanol.
4. The method for preparing the polyimide composite film material according to claim 1, wherein the end-capping agent is isophthalic acid.
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