CN117210155A - Self-cleaning anti-pollution energy-saving film for building and preparation method thereof - Google Patents
Self-cleaning anti-pollution energy-saving film for building and preparation method thereof Download PDFInfo
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- CN117210155A CN117210155A CN202311196552.XA CN202311196552A CN117210155A CN 117210155 A CN117210155 A CN 117210155A CN 202311196552 A CN202311196552 A CN 202311196552A CN 117210155 A CN117210155 A CN 117210155A
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- 238000004140 cleaning Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000010410 layer Substances 0.000 claims abstract description 78
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 70
- 239000012790 adhesive layer Substances 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000011241 protective layer Substances 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011247 coating layer Substances 0.000 claims abstract description 20
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 19
- 229910052786 argon Inorganic materials 0.000 claims abstract description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 11
- 238000009434 installation Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 81
- 239000004593 Epoxy Substances 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- 238000001723 curing Methods 0.000 claims description 13
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 238000003848 UV Light-Curing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 16
- 230000003287 optical effect Effects 0.000 abstract description 7
- 239000012528 membrane Substances 0.000 abstract description 4
- 238000007747 plating Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 150000002576 ketones Chemical class 0.000 description 10
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 9
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- -1 argon ions Chemical class 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000012780 transparent material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- PVJDYCWESWOLKI-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(O)C(CC)(CO)CO.OCC(O)CO Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(O)C(CC)(CO)CO.OCC(O)CO PVJDYCWESWOLKI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
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- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
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Abstract
The application relates to the technical field of protective films, in particular to the field of IPC C08L27, and more particularly relates to a self-cleaning anti-pollution energy-saving film for buildings and a preparation method thereof. The structure of energy-conserving membrane includes from the top down in proper order: an upper protective layer, a titanium dioxide layer, a barrier composite adhesive layer, a PET substrate layer, an installation adhesive layer and a lower protective layer. The titanium dioxide layer comprises a substrate layer and a titanium dioxide coating layer, and the thickness ratio of the substrate layer to the titanium dioxide coating layer is 25: (0.3-0.7), can improve the anti-fouling cleaning performance, improve the visible light transmittance at the same time, and reduce the optical distortion; the parameters of the magnetron sputtering comprise oxygen flow and argon flow, and the ratio of the oxygen flow to the argon flow is 1: (1-2) can improve the hydrophilicity and uniformity of the plating layer, and further improve the cleaning performance.
Description
Technical Field
The application relates to the technical field of protective films, in particular to the field of IPC C08L27, and more particularly relates to a self-cleaning anti-pollution energy-saving film for buildings and a preparation method thereof.
Background
In recent years, transparent materials such as glass are increasingly used in the fields of buildings, vehicles, boats and the like, the high permeability of the transparent materials to solar radiation greatly aggravates the refrigeration and heating energy consumption of an inner space, and meanwhile, the regular cleaning of the glass also needs to cost more. More and more researches are carried out on the way of changing the light transmittance, the ultraviolet resistance and the self-cleaning property of glass through a composite protective film, and the way of organically combining titanium dioxide with the glass is the current research direction, and under the prior art condition, the problems of long time, uneven titanium dioxide dispersion, different particle sizes and low raw material utilization rate exist in the traditional sedimentation method.
CN105002656B discloses a hydrophobic membrane, in particular a hydrophobic membrane with self-cleaning function, a preparation method and application thereof, a polymer nanofiber membrane prepared by electrostatic spinning technology, the surface of which is modified by titanium dioxide to improve the surface hydrophobicity; the contact angle of the hydrophobic film with water reaches 140-180 degrees. The prepared hydrophobic film has a self-cleaning function, but affects the visible light transmittance at the same time, so that the application of the hydrophobic film on the surface of a transparent material is limited.
Disclosure of Invention
The first aspect of the application provides a self-cleaning anti-pollution energy-saving film for buildings, which comprises the following components in sequence from top to bottom: an upper protective layer, a titanium dioxide layer, a barrier composite adhesive layer, a PET substrate layer, an installation adhesive layer and a lower protective layer.
Preferably, the thickness of the upper protective layer is 23-80 μm.
The upper protective layer comprises a release film made of silica gel.
Preferably, the release film is a PET silica gel release film, which is purchased from Siveli high-tech Co., ltd.
Preferably, the PET substrate layer has a thickness of 28-50 μm.
The PET substrate layer comprises a PET transparent film, and is purchased from Mingtai, model: G01.
preferably, the thickness of the mounting adhesive layer is 8-30 mu m.
Preferably, the mounting adhesive layer comprises acrylate pressure sensitive adhesive.
Preferably, the acrylate pressure sensitive adhesive is available from bang rui, model: LK22.
Preferably, the thickness of the lower protective layer is 23-50 μm.
The lower protective layer comprises a polyester film or a release film.
Preferably, the polyester comprises one of PET, PEN, PBT, PTT.
Further preferably, the lower protective layer comprises a polyester release film PET, with a thickness of 23 μm, available from various optodes, model number, of yangzhou: C05-T1.
The thickness of the titanium dioxide layer is 25-50 mu m.
The titanium dioxide layer comprises a substrate layer and a titanium dioxide coating layer, and the thickness ratio of the substrate layer to the titanium dioxide coating layer is 25: (0.3-0.7), the anti-fouling cleaning performance can be improved, the visible light transmittance can be improved, and the optical distortion can be reduced. The titanium dioxide layer comprises a substrate layer and a titanium dioxide coating, and the thickness ratio of the substrate layer to the titanium dioxide coating is 25: (0.3-0.7), while improving the anti-fouling performance, simultaneously improving the visible light transmittance and reducing the optical distortion. The titanium dioxide coating surface has excellent self-cleaning anti-fouling performance, and is easier to clean than an untreated surface, because the photocatalytic property of the titanium dioxide can decompose and oxidize organic substances attached to the surface under the action of ultraviolet rays in sunlight, so that the surface cleanliness is remarkably improved. Meanwhile, under the action of ultraviolet light, the titanium dioxide film also can generate hydrophilic and oleophilic amphoteric characteristics, so that organic matters attached to the surface can be easily washed away by rainfall or other naturally generated water, the cleaning effect is achieved, as the thickness of the titanium dioxide coating is further increased, the visible light transmittance is reduced, the indoor brightness is reduced, meanwhile, the light distortion is also increased due to the excessive thickness, possibly, as the compactness of the titanium dioxide coating is improved, the composite performance of the composite adhesive layer is reduced, meanwhile, the curing time of the composite adhesive layer is prolonged, a multi-curvature curved surface is also generated, and the light distortion is generated.
Preferably, the titanium dioxide layer comprises a substrate layer and a titanium dioxide coating layer, and the thickness ratio of the substrate layer to the titanium dioxide coating layer is 25: (0.3-0.7).
The thickness of the substrate layer is 12.5-50 mu m.
The substrate layer comprises one of polyimide film and PET film.
Preferably, the substrate layer comprises a polyimide film having a thickness of 25 μm, available from Taihu Hei New Material science and technology Co., ltd., model:JL。
the preparation process of the titanium dioxide coating layer comprises magnetron sputtering.
The preparation raw materials of the titanium dioxide coating layer comprise target materials with the purity of 99.9-99.99%, working gas with the purity of 99.99-99.999% and reaction gas with the purity of 99.99-99.999%.
Preferably, the raw materials for preparing the titanium dioxide coating layer comprise a target material with the purity of 99.99%, working gas with the purity of 99.999% and reaction gas with the purity of 99.999%.
Preferably, the target is Ti, the working gas is Ar, and the reaction gas is O 2 。
Preferably, the working temperature of the magnetron sputtering is 250-300 ℃.
The parameters of the magnetron sputtering comprise oxygen flow and argon flow, and the ratio of the oxygen flow to the argon flow is 1: (1-2) can improve the hydrophilicity and uniformity of the plating layer, and further improve the cleaning performance. The application has found that TiO 2 The stoichiometry of titanium to oxygen in the film will vary with the argon-oxygen ratio. When the oxygen flow is too small, argon ions are usedThe titanium atoms and oxygen ions sputtered out do not react sufficiently, so that the titanium dioxide crystal structure is not easy to form, when the oxygen flow is too large, the surface of the target material is changed from a conversion mode to a reaction mode, so that the surface of the target material is highly oxidized, the sputtering amount and the deposition rate are reduced, and as the oxygen flow is increased, the film becomes rough and loose, the risk of generating holes is increased, and meanwhile, under the condition of higher oxygen partial pressure, the TiO is easily caused due to the fact that the oxygen is too sufficient 2 Oxygen vacancies in the film decrease, resulting in a decrease in the photohydrophilic properties of the film. The ratio of oxygen flow to argon flow is 1: (1-2) effective increase of TiO 2 Specific surface area of the film, effective surface area of the film is increased, and TiO is further improved 2 The film has strong hydrophilic performance, so that a uniform water film is formed when water vapor is condensed, and the aggregation of water drops is prevented, so that the light scattering is avoided. In addition, the film after spreading is thinner and is easier to volatilize quickly, so that the cleanliness of the surface is further improved.
The parameters of the magnetron sputtering comprise oxygen flow and argon flow, and the ratio of the oxygen flow to the argon flow is 1: (1-2).
Preferably, the oxygen flow is 10-15sccm.
Preferably, the argon flow is 13-17sccm.
Preferably, the thickness of the titanium dioxide coating layer is 0.3-0.65 mu m.
The inventors found that the thickness ratio of the titanium dioxide layer to the barrier composite glue layer is (25-65): (10-30), can effectively balance visible light transmittance, ultraviolet transmittance and self-cleaning anti-fouling performance. With the increase of the thickness of the barrier composite adhesive layer, the ultraviolet transmittance is reduced, but the visible light transmittance is reduced, the light transmittance is influenced, and with the increase of the thickness of the titanium dioxide layer, the self-cleaning anti-fouling performance is increased, but the visible light transmittance of the barrier composite adhesive layer is influenced, the titanium dioxide layer and the barrier composite adhesive layer are possibly subjected to ultraviolet curing after being compounded in the preparation process, and the titanium dioxide layer is subjected to certain blocking on ultraviolet light penetration, so that the curing uniformity of the composite adhesive layer is influenced, particularly the too thick barrier composite adhesive layer can lead to further reduction of the curing performance, the probability of light distortion is increased, meanwhile, the light transmittance of the titanium dioxide layer is poorer, and the too high thickness can lead to the increase of the compactness of the titanium dioxide layer to influence the composite performance and also influence on the visible light projection.
Preferably, the thickness ratio of the titanium dioxide layer to the barrier composite adhesive layer is (25-65): (10-30).
The preparation raw materials of the barrier composite adhesive layer comprise the following components in percentage by weight: 50-80% of acrylate monomer, 0.5-5% of photoinitiator, 1-10% of active agent, 8-15% of cross-linking agent, 0.1-5% of additive, 0.3-1% of ultraviolet absorber, 0.3-0.5% of infrared absorber and the balance of solvent.
Preferably, the preparation raw materials of the barrier composite adhesive layer comprise the following components in percentage by weight: 60-70% of acrylate monomer, 0.5-2% of photoinitiator, 1-5% of active agent, 8-13% of cross-linking agent, 0.1-2% of additive, 0.3-0.8% of ultraviolet absorber, 0.3-0.4% of infrared absorber and the balance of solvent.
Further preferably, the preparation raw materials of the barrier composite adhesive layer comprise, by weight: 70% of acrylate monomer, 0.8% of photoinitiator, 3% of active agent, 12% of cross-linking agent, 0.5% of additive, 0.4% of ultraviolet absorber, 0.35% of infrared absorber and the balance of solvent.
The acrylate monomer comprises a soft monomer, a hard monomer and an epoxy monomer, wherein the weight ratio of the soft monomer to the hard monomer to the epoxy monomer is 1: (0.2-0.5): (0.1-0.2), the mechanical property and the stability of the film layer can be improved, the composite property with the titanium dioxide layer can be improved, and the optical distortion can be reduced. The weight part ratio of the soft monomer to the hard monomer to the epoxy monomer in the monomer component is 1: (0.2-0.5): (0.1-0.2). When the film is used for building glass, the mechanical property and the stability of the film can be improved, the composite property of the film and the titanium dioxide layer can be improved, the optical distortion is reduced, the film has certain flexibility due to the soft monomer, the stability of the film can be improved within a certain range, and the film is particularly applied to building glass and is subjected to high-temperature or low-temperature environment for a long time, so that the requirement on the stability of the film is higher. However, an excessively large proportion results in a decrease in film forming property, tackiness of the coating film surface, and a decrease in high-temperature stability. With the increase of the proportion of the hard monomer, the hard monomer has larger steric hindrance, so that the mechanical properties such as the hardness of the film layer are correspondingly improved, but when the content is too high, the polymerization force in the film layer is too large, and the film layer becomes brittle. The addition of the epoxy monomer improves the toughness of the film and the composite performance of the titanium dioxide layer, but when the content of the epoxy monomer is too much, the weather resistance and ultraviolet light resistance of the film layer are poor due to benzene rings in the epoxy monomer, and excessive benzene rings can reduce interlayer adhesive force and easily increase the risk of optical distortion. It is possible that the epoxy monomer creates a greater steric hindrance, impeding the efficient chemical collision of the curing agent with the epoxy group, increasing the risk of volume shrinkage from post-curing.
The acrylate monomer comprises a soft monomer, a hard monomer and an epoxy monomer, wherein the weight ratio of the soft monomer to the hard monomer to the epoxy monomer is 1: (0.2-0.5): (0.1-0.2).
Preferably, the acrylate monomer comprises a soft monomer, a hard monomer and an epoxy monomer, wherein the weight ratio of the soft monomer to the hard monomer to the epoxy monomer is 1:0.3:0.1.
preferably, the soft monomer includes one or more of butyl acrylate, methyl acrylate, acrylic acid, ethyl acrylate, 2-hydroxyethyl acrylate, isooctyl methacrylate, and lauryl acrylate.
Further preferably, the soft monomer comprises butyl acrylate and methyl acrylate, and the weight ratio of the butyl acrylate to the methyl acrylate is 1: (2-5).
Still more preferably, the soft monomer comprises butyl acrylate and methyl acrylate, and the weight ratio of the butyl acrylate to the methyl acrylate is 1:3.
preferably, the hard monomer comprises one or more of styrene, methyl methacrylate, vinyl acetate and vinyl chloride.
Further preferably, the hard monomer comprises methyl methacrylate.
Preferably, the epoxy monomer includes one of bisphenol a epoxy monomer and bisphenol F epoxy monomer.
Further preferably, the epoxy monomer comprises bisphenol a epoxy monomer, trade name E12, available from baling petrochemicals.
Preferably, the active agent is methyl 2-methyl-1-acrylate.
The cross-linking agent comprises one of trimethylolpropane tri (methyl) acrylate, glycerol trimethylolpropane triacrylate, pentaerythritol tetraacrylate, di (trimethylolpropane) tetraacrylate, polydipentaerythritol pentaacrylate and polydipentaerythritol hexaacrylate.
Preferably, the cross-linking agent comprises trimethylolpropane tri (methyl) acrylate and pentaerythritol tetraacrylate, and the weight ratio of the trimethylolpropane tri (methyl) acrylate to the pentaerythritol tetraacrylate is (3-5): 1.
further preferably, the crosslinking agent comprises trimethylolpropane tri (meth) acrylate and pentaerythritol tetraacrylate, wherein the weight ratio of the trimethylolpropane tri (meth) acrylate to the pentaerythritol tetraacrylate is 5:1.
preferably, the photoinitiator comprises a ketone photoinitiator and a peroxy photoinitiator, and the weight ratio of the ketone photoinitiator to the peroxy photoinitiator is 1: (0.2-0.6).
Further preferably, the photoinitiator comprises a ketone photoinitiator and a peroxy photoinitiator, and the weight ratio of the ketone photoinitiator to the peroxy photoinitiator is 1:0.3.
the ketone photoinitiator comprises one of diphenyl ketone, 4-phenylbenzophenone, p-chlorobenzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2-hydroxy-2-methyl-1- [4- (tertiary butyl) phenyl ] -1-acetone.
Preferably, the ketone photoinitiator comprises 4-phenylbenzophenone.
The peroxy photoinitiator comprises one of tert-butyl peroxybenzoate, dicumyl peroxide and dibenzoyl peroxide.
Preferably, the peroxy-based photoinitiator comprises t-butyl peroxybenzoate.
The solvent comprises one of an alcohol solvent, an ester solvent, an ether solvent and a ketone solvent.
Preferably, the solvent comprises an ester solvent.
Preferably, the ester solvent comprises ethyl acetate.
Preferably, the additive comprises an antifoaming agent.
Preferably, the defoamer is a silicone defoamer available from basf, model FoamStar SI 2210.
The ultraviolet absorbent comprises one of diphenyl ketone, salicylate, benzotriazole, triazine and substituted acrylonitrile.
Preferably, the ultraviolet absorber comprises a benzotriazole type ultraviolet absorber.
Preferably, the benzotriazole ultraviolet absorber comprises one of UV-326, UV-327.
Further preferably, the benzotriazole-based ultraviolet absorber comprises UV-326 (CAS: 3896-11-5).
The infrared absorber comprises a near infrared absorber and a far infrared absorber, and the absorption wavelength is from 710nm to 1085nm.
Preferably, the infrared absorbing agent is IR-710, IR-850, IR-960, and the weight ratio of IR-710, IR-850, IR-960 is 1: (2-3): (2-4).
Further preferably, the infrared absorbing agent is IR-710, IR-850, IR-960, and the weight ratio of IR-710, IR-850, IR-960 is 1:2:2.5.
the application provides a preparation method of a self-cleaning anti-pollution energy-saving film for a building, which comprises the following steps of:
s1, coating an installation adhesive layer on the lower surface of a PET substrate layer, and after drying, compounding a lower protective layer;
s2, coating a barrier composite adhesive layer on the PET substrate layer;
s3, compounding the substrate layer surface of the titanium dioxide layer with the barrier composite adhesive layer, and performing UV curing;
and S4, compounding the upper protective layer with the titanium dioxide coating surface of the titanium dioxide layer to obtain the titanium dioxide coating.
The light intensity of the solidification is 70-100W/m 2 The curing time is 3-6s.
Preferably, the light intensity of the curing is 80W/m 2 The curing time was 4s.
The beneficial effects are that:
1. the titanium dioxide layer comprises a substrate layer and a titanium dioxide coating layer, and the thickness ratio of the substrate layer to the titanium dioxide coating layer is 25: (0.3-0.7), the anti-fouling cleaning performance can be improved, the visible light transmittance can be improved, and the optical distortion can be reduced.
2. The parameters of the magnetron sputtering comprise oxygen flow and argon flow, and the ratio of the oxygen flow to the argon flow is 1: (1-2) can reduce the contact angle, improve the hydrophilicity and uniformity of the coating, and further improve the cleaning performance.
3. The thickness ratio of the titanium dioxide layer to the barrier composite adhesive layer is (25-65): (10-30), can effectively balance visible light transmittance, ultraviolet transmittance and self-cleaning anti-fouling performance.
4. The acrylate monomer comprises a soft monomer, a hard monomer and an epoxy monomer, wherein the weight ratio of the soft monomer to the hard monomer to the epoxy monomer is 1: (0.2-0.5): (0.1-0.2), the mechanical property and the stability of the film layer can be improved, and the composite property with the titanium dioxide layer can be improved.
5. The light intensity of the solidification is 70-100W/m 2 The curing time is 3-6s, so that the curing efficiency can be further improved, and the composite performance with the titanium dioxide layer can be improved.
Drawings
FIG. 1 is a self-cleaning anti-fouling energy-saving film structure for building according to example 1, wherein 1 is an upper protective layer; 2. a titanium dioxide layer; 3. a barrier composite adhesive layer; 4. a PET substrate layer; 5. installing an adhesive layer; 6. and a lower protective layer.
Detailed Description
Example 1
The utility model provides a building self-cleaning anti-soil energy-saving film, the structure of energy-saving film, from the top down is in proper order: an upper protective layer 1, a titanium dioxide layer 2, a barrier composite adhesive layer 3, a PET substrate layer 4, an installation adhesive layer 5 and a lower protective layer 6.
The upper protective layer 1 is a release film made of silica gel.
The release film is a PET silica gel release film with the thickness of 50 μm and is purchased from Siveli high-tech Co., tianjin.
The PET substrate layer 4 is a PET transparent film with the thickness of 50 mu m and is purchased from Mingtai, yangzhou, model: G01.
the thickness of the installation adhesive layer 5 is 10 mu m, the installation adhesive layer 5 is an acrylic pressure-sensitive adhesive, and the acrylic pressure-sensitive adhesive is purchased from Hengzhou Pond, model: LK22.
The lower protective layer 6 is a polyester release film PET with the thickness of 23 mu m and is purchased from Yangzhou Wanchun photoelectric products, model: C05-T1.
The titanium dioxide layer 2 comprises a substrate layer and a titanium dioxide coating layer
The substrate layer is a polyimide film with the thickness of 25 mu m and is purchased from Taihu Hezhi New Material science and technology Co., ltd., model:JL。
the preparation method of the titanium dioxide coating layer comprises the following steps of: the method comprises the steps of adding a magnetic field on the surface of a target, accelerating charged ions in the magnetic field, then carrying out a certain kinetic energy, and carrying out emission collision with sputtering gas atoms to ionize a large amount of Ar+ and electrons, wherein Ar+ bombards the target, the sputtered target atoms are deposited on a substrate to form a film, the preparation raw material of the titanium dioxide coating layer is a target with the purity of 99.99%, working gas with the purity of 99.999%, reaction gas with the purity of 99.999%, the target is Ti, the working gas is Ar, and the reaction gas is O 2 。
The working temperature of the magnetron sputtering is 250 ℃, the oxygen flow is 10sccm, the argon flow is 15sccm, and the thickness of the titanium dioxide coating layer is 0.33 μm.
The thickness of the barrier composite glue layer 3 is 15 μm.
The preparation raw materials of the barrier composite adhesive layer 3 are as follows: 70% of acrylate monomer, 0.8% of photoinitiator, 3% of active agent, 12% of cross-linking agent, 0.5% of additive, 0.4% of ultraviolet absorber, 0.35% of infrared absorber and the balance of solvent.
The acrylate monomer is a soft monomer, a hard monomer and an epoxy monomer, and the weight ratio of the soft monomer to the hard monomer to the epoxy monomer is 1:0.3:0.1, wherein the soft monomer is butyl acrylate and methyl acrylate, and the weight ratio of the butyl acrylate to the methyl acrylate is 1: and 3, the hard monomer is methyl methacrylate, the epoxy monomer is bisphenol A epoxy monomer, the brand is E12, and the epoxy monomer is purchased from Baling petrochemical industry.
The active agent is 2-methyl-1-methyl acrylate.
The cross-linking agent is trimethylolpropane tri (methyl) acrylate or pentaerythritol tetraacrylate, and the weight ratio of the trimethylolpropane tri (methyl) acrylate to the pentaerythritol tetraacrylate is 5:1.
the photoinitiator is a ketone photoinitiator and a peroxy photoinitiator, and the weight ratio of the ketone photoinitiator to the peroxy photoinitiator is 1:0.3, wherein the ketone photoinitiator is 4-phenylbenzophenone, and the peroxy photoinitiator is tert-butyl peroxybenzoate.
The solvent is ethyl acetate.
The additive is an antifoaming agent, which is an organosilicon antifoaming agent available from basf, model FoamStar SI 2210.
The ultraviolet absorber is benzotriazole ultraviolet absorber, and the benzotriazole ultraviolet absorber is UV-326 (CAS: 3896-11-5).
The infrared absorbing agent is IR-710, IR-850 and IR-960, and the weight ratio of the IR-710, the IR-850 and the IR-960 is 1:2:2.5.
the preparation of the barrier composite adhesive layer 3 comprises the following steps of; sequentially adding an acrylic ester monomer, a photoinitiator, an active agent, a crosslinking agent, an additive, an ultraviolet absorber and an infrared absorber into a solvent, and stirring at 200rpm in a dark place for 30min.
The preparation method of the self-cleaning anti-fouling energy-saving film for the building comprises the following steps:
s1, coating an installation adhesive layer 5 on the lower surface of a PET substrate layer 4, drying, and pressing and attaching the lower protective layer 6 by a pressing roller to form a composite film;
s2, coating a barrier composite adhesive layer 3 on the PET substrate layer 4;
s3, compounding the substrate layer surface of the titanium dioxide layer 2 with the barrier composite adhesive layer 3, and performing UV curing;
s4, compounding the titanium dioxide coating surfaces of the upper protective layer 1 and the titanium dioxide layer 2 to obtain the titanium dioxide coating.
The light intensity of the curing is 80W/m 2 The curing time was 4s.
Example 2
The detailed description is the same as example 1; in example 2, the magnetron sputtering was operated at 300℃and the thickness of the titanium oxide plating film was 0.46. Mu.m.
Example 3
The detailed description is the same as example 1; in example 3, the magnetron sputtering was operated at 300℃and the oxygen flow was 15sccm, and the thickness of the titanium oxide film was 0.62. Mu.m.
Comparative example 1
The detailed description is the same as example 1; except that in comparative example 1: the oxygen flow rate was 15sccm and the argon flow rate was 10ccm.
Comparative example 2
The detailed description is the same as example 1; except that in comparative example 2: the acrylate monomer comprises a soft monomer, a hard monomer and an epoxy monomer, wherein the weight ratio of the soft monomer to the hard monomer to the epoxy monomer is 1:0.1:0.3.
performance test method and data
TABLE 1
Claims (10)
1. The utility model provides a building self-cleaning anti-soil energy-saving film which characterized in that, the structure of energy-saving film includes from the top down in proper order: an upper protective layer, a titanium dioxide layer, a barrier composite adhesive layer, a PET substrate layer, an installation adhesive layer and a lower protective layer.
2. The self-cleaning anti-fouling energy-saving building film according to claim 1, wherein the titanium dioxide layer comprises a substrate layer and a titanium dioxide coating layer, and the thickness ratio of the substrate layer to the titanium dioxide coating layer is 25: (0.3-0.7).
3. The self-cleaning anti-fouling energy-saving film for buildings according to claim 2, wherein the preparation process of the titanium dioxide coating layer comprises magnetron sputtering.
4. A self-cleaning anti-fouling energy-saving film for buildings according to claim 3, wherein the parameters of the magnetron sputtering comprise oxygen flow and argon flow, and the ratio of the oxygen flow to the argon flow is 1:
(1-2)。
5. the self-cleaning anti-fouling energy-saving film for buildings according to claim 4, wherein the thickness of the titanium dioxide coating layer is 0.3-0.65 μm.
6. The self-cleaning anti-fouling energy-saving film for buildings according to claim 5, wherein the thickness ratio of the titanium dioxide layer to the barrier composite glue layer is (25-65): (10-30).
7. The self-cleaning anti-fouling energy-saving building film according to claim 6, wherein the preparation raw materials of the barrier composite adhesive layer comprise, in weight percent: 50-80% of acrylate monomer, 0.5-5% of photoinitiator, 1-10% of active agent, 8-15% of cross-linking agent, 0.1-5% of additive, 0.3-1% of ultraviolet absorber, 0.3-0.5% of infrared absorber and the balance of solvent.
8. The self-cleaning anti-fouling energy-saving building film according to claim 7, wherein the acrylate monomer comprises a soft monomer, a hard monomer and an epoxy monomer, and the weight ratio of the soft monomer to the hard monomer to the epoxy monomer is 1: (0.2-0.5): (0.1-0.2).
9. A method for preparing the self-cleaning anti-fouling energy-saving building film according to claim 8, which comprises the following steps:
s1, coating an installation adhesive layer on the lower surface of a PET substrate layer, and after drying, compounding a lower protective layer;
s2, coating a barrier composite adhesive layer on the PET substrate layer;
s3, compounding the substrate layer surface of the titanium dioxide layer with the barrier composite adhesive layer, and performing UV curing;
and S4, compounding the upper protective layer with the titanium dioxide coating surface of the titanium dioxide layer to obtain the titanium dioxide coating.
10. The method for preparing the self-cleaning anti-fouling energy-saving film for the building according to claim 9, wherein the light intensity of the solidification is 70-100W/m 2 The curing time is 3-6s.
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