CN117362729A - Weather-resistant deformation-resistant colorful film for plate and preparation method thereof - Google Patents
Weather-resistant deformation-resistant colorful film for plate and preparation method thereof Download PDFInfo
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- CN117362729A CN117362729A CN202311378832.2A CN202311378832A CN117362729A CN 117362729 A CN117362729 A CN 117362729A CN 202311378832 A CN202311378832 A CN 202311378832A CN 117362729 A CN117362729 A CN 117362729A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 125000003003 spiro group Chemical group 0.000 claims abstract description 20
- 238000000016 photochemical curing Methods 0.000 claims abstract description 19
- 229920002799 BoPET Polymers 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 12
- 239000004814 polyurethane Substances 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 43
- -1 amino hydroxyl Chemical group 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 21
- 229920002545 silicone oil Polymers 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 20
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 238000005269 aluminizing Methods 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 5
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical group OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000004313 glare Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- 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
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08J2475/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a weather-resistant anti-deformation colorful film for a plate and a preparation method thereof, and relates to the technical field of functional films. The weather-resistant anti-deformation colorful plate film comprises a base layer, a UV coating and an aluminum layer, wherein the base layer is a self-made PET film, the UV coating is a composite ink coating, and the aluminum layer is a vacuum aluminized layer; the self-made PET film is prepared by introducing a dihydroxy monomer containing a spiro structure into PET to serve as a pre-modified monomer, adding epoxy polypentadiene to prepare the self-made PET film, enhancing the bonding force of the colorful film, and enhancing the weather resistance and mechanical properties of the colorful film, wherein the composite ink coating comprises a photo-curing component and an ink component; the photo-curing component comprises a photo-initiator and modified styrene-acrylic emulsion, and the printing ink component is polyurethane acrylate oligomer, so that the mechanical property is enhanced, and the anti-deformation property of the colorful film is improved.
Description
Technical Field
The invention relates to the technical field of functional films, in particular to a weather-resistant anti-deformation colorful film for a plate and a preparation method thereof.
Background
The thin film for decoration is printed by common printing ink, vacuum deposited multilayer inorganic thin film, and coated liquid crystal or coated color-changing powder, etc. in the prior art, the colorful effect is improved, namely, different colors or metallic luster effects can be presented under the condition of different visual angles, so that the home decoration has interestingness.
The colorful film taking PET as the base material often has the problems of insufficient weather resistance, insufficient deformation resistance and the like, and limits the application range of the colorful film prepared by taking PET as the base material. Therefore, the invention researches and prepares the weather-resistant anti-deformation colorful film with excellent weather resistance and deformation resistance for the board, so as to expand the application range of the weather-resistant anti-deformation colorful film for the board.
Disclosure of Invention
The invention aims to provide a weather-resistant anti-deformation colorful film for a plate and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the weather-resistant deformation-resistant colorful film comprises a base layer, a UV coating and an aluminum layer; the base layer is a self-made PET film; the UV coating is a composite ink coating; the aluminum layer is a vacuum aluminum plating layer.
Preferably, the self-made PET film is prepared by introducing a dihydroxy monomer containing a spiro structure into PET to serve as a pre-modified monomer and then adding epoxy polypentadiene.
Preferably, the composite ink coating includes a photocurable component and an ink component; the light curing component comprises a photoinitiator and modified styrene-acrylic emulsion; the ink component is a urethane acrylate oligomer.
Preferably, the modified styrene-acrylic emulsion is prepared by introducing amino hydroxyl silicone oil into styrene-acrylic emulsion; the polyurethane acrylate oligomer is prepared by taking polytetrahydrofuran as long carbon chain diol.
Preferably, the preparation method of the weather-resistant anti-deformation colorful film comprises the following specific steps:
(1) Mixing terephthalic acid, ethylene glycol, isopropyl titanate and a dihydroxyl monomer containing a spiro structure according to a mass ratio of 1:1.3-1.5:0.04-0.06:0.25-0.35 in a nitrogen atmosphere, heating to 220-240 β, reacting for 3-5 h, heating to 250-260 β, adjusting the pressure to 0.06-0.08 MPa, adding epoxy polypentadiene with the mass of 0.2-0.4 times of that of terephthalic acid, continuously reacting for 2-4 h, heating to 270-280 β, continuously reacting for 3-4 h, discharging, and cooling to room temperature to obtain self-made PET; casting the self-made PET by an extruder, and stretching the self-made PET by a biaxial static stretcher at 92-95 β with a stretching ratio of 4.2-4.4 to obtain a self-made PET film, namely a base layer;
(2) Mixing deionized water, sodium dodecyl sulfonate, styrene, butyl acrylate, polyoxyethylene octyl ether and amino hydroxyl silicone oil according to the mass ratio of 60-80:3:44:45:1:9-11, heating to 55-58 β, stirring at 100-400 rpm for reaction, performing seed polymerization reaction after 30-50 min, heating to 65-68 β, reacting for 30-40 min, adding ammonium persulfate solution with the mass fraction of 3-5% and the mass fraction of 0.3-0.6 times that of the amino hydroxyl silicone oil, heating to 70-72 β for reaction for 50-90 min, heating to 75-78 β for reaction for 50-90 min, cooling to 40-45 β, regulating pH to 7.8-8.2 with sodium hydroxide, and finally filtering with a 180-mesh screen to obtain modified styrene-acrylic emulsion; mixing the modified styrene-acrylic emulsion and a photoinitiator 184 according to a mass ratio of 8-12:1, and uniformly stirring to obtain a photocuring component;
(3) Mixing 4, 4-dicyclohexylmethane diisocyanate and polytetrahydrofuran under the nitrogen atmosphere, heating to 60-62 β, uniformly stirring, adding dibutyltin dilaurate with the mass of 0.004-0.006 times that of polytetrahydrofuran, continuously reacting for 5-6 h, adding hydroxyethyl acrylate with the mass of 0.3-0.4 times that of polytetrahydrofuran, heating to 70-72 β, and continuously reacting for 4-6 h to obtain polyurethane acrylate oligomer, namely an ink component;
(4) Mixing the photo-curing component with the ink component to prepare a composite ink; uniformly coating composite ink on the surface of the base layer, wherein the coating amount is 0.3-0.5 g/m 2 Ultraviolet curing is carried out at 60-70 β to obtain a colorful film; and finally, aluminizing the surface of the colorful film by using a vacuum aluminizing machine to obtain the weather-resistant deformation-resistant colorful film for the plate.
Preferably, in the step (1): the preparation method of the dihydroxy monomer containing the spiro structure comprises the following steps: bisphenol A and methanesulfonic acid are mixed according to the mass ratio of 1-1.2:5, stirred for 3-4 d at 100-200 rpm, transferred into ice water, stirred uniformly, filtered by suction, washed for 8-12 times by deionized water, and recrystallized by ethanol solution with the mass fraction of 30-60%, thus obtaining the dihydroxy monomer with the spiro structure.
Preferably, in the step (1): the preparation method of the epoxy polypentadiene comprises the following steps: mixing naphthalene, sodium and tetrahydrofuran according to a mass ratio of 1:1:20-30 in a nitrogen atmosphere, and stirring until the mixture is black and green to prepare a naphthalene sodium complex initiator; mixing cyclohexene, isoprene and sodium naphthalene complex initiator according to the mass ratio of 2-3:1:0.04-0.08, heating to 60-80 β, stirring at 100-200 rpm for reaction for 2-4 h, adding ethylene glycol diglycidyl ether with the mass of 0.3-0.5 times of cyclohexene, continuing to react for 3-6 h, terminating the reaction with ethanol, and finally drying in a vacuum drying oven to constant weight to obtain the epoxy polypentadiene.
Preferably, in the step (2): the preparation method of the amino hydroxyl silicone oil comprises the following steps: mixing the emulsifier A170 with deionized water according to the mass ratio of 1:15-20, stirring uniformly, adding octamethyl cyclotetrasiloxane with the mass ratio of 8-10 times that of the emulsifier A170, stirring at 2000-4000 rpm for 40-60 min, heating to 80-85 β, continuing stirring for reacting for 3-6 h, adding dibutyltin dilaurate with the mass ratio of 0.03-0.06 times that of the emulsifier A170 and aminosilane 602 with the mass ratio of 4-6 times that of the emulsifier A170, continuing reacting for 3-6 h, cooling to 40-50 β, regulating the pH to 6.5-6.8 by using glacial acetic acid, and performing rotary evaporation to obtain the amino hydroxyl silicone oil.
Preferably, in the step (3): the mass ratio of the 4, 4-dicyclohexylmethane diisocyanate to the polytetrahydrofuran is 13-15:50.
Preferably, in the step (4): the mass ratio of the photo-curing component to the ink component is 1:18-25.
Compared with the prior art, the invention has the following beneficial effects:
the weather-resistant anti-deformation colorful plate film comprises a base layer, a UV coating and an aluminum layer, wherein the base layer is a self-made PET film, the UV coating is a composite ink coating, and the aluminum layer is a vacuum aluminized layer;
the self-made PET film is prepared by introducing a dihydroxy monomer containing a spiro structure into PET to serve as a pre-modified monomer, and then adding epoxy polypentadiene; the spiro structure is introduced into the PET structure, so that the rigid structure on the PET molecular chain is increased, the weather resistance and the mechanical property are enhanced, the colorful film is prevented from being deformed by external force, a microporous structure can be formed in the PET, an adsorption effect is generated on the plate, and the adhesive force of the colorful film is enhanced; then introducing epoxy polypentadiene to react with active groups on PET and dihydroxyl monomers to form a tighter cross-linked structure, so that the weather resistance of the colorful film is further enhanced;
the composite ink coating includes a photocurable component and an ink component; the photo-curing component comprises a photo-initiator and modified styrene-acrylic emulsion, and the ink component is polyurethane acrylate oligomer; the modified styrene-acrylic emulsion is prepared by introducing amino hydroxyl silicone oil into the styrene-acrylic emulsion, and the polyurethane acrylate oligomer is prepared by taking polytetrahydrofuran as long carbon chain diol, has higher flexibility and crosslinking density, can continuously react with the modified styrene-acrylic emulsion after being blended with a photocuring component, and introduces the styrene-acrylic emulsion with strong adhesive property into a UV coating, so that the adhesive force of the composite ink coating to a base layer and a vacuum aluminized layer is enhanced, and the mechanical property is enhanced, thereby improving the deformation resistance of a colorful film.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the test methods of each index of the weather-resistant anti-deformation colorful film of the plate prepared in the examples and the comparative examples are as follows:
weather resistance: the weather-resistant anti-deformation colorful films of the plates prepared in the examples and the comparative examples are referred to GB/T2423.3, and the retention rate of the mechanical properties is 85 β at 85% humidity for 3000 hours.
Mechanical properties: the weather-resistant anti-deformation colorful films of the plates prepared in the examples and the comparative examples are subjected to tensile strength test by referring to ISO 527-3.
Adhesive force: the weather-resistant anti-deformation colorful films of the plates prepared in the examples and the comparative examples are subjected to adhesion test at normal temperature by referring to GB/T2792.
Example 1
(1) Mixing bisphenol A and methanesulfonic acid according to a mass ratio of 1:5, stirring for 3d at 100rpm, transferring into ice water, stirring uniformly, carrying out suction filtration, washing with deionized water for 8 times, and recrystallizing with 30% ethanol solution to obtain a dihydroxy monomer with a spiro structure; mixing naphthalene, sodium and tetrahydrofuran according to a mass ratio of 1:1:20 under a nitrogen atmosphere, and stirring until the mixture is black and green to prepare a naphthalene sodium complex initiator; mixing cyclohexene, isoprene and sodium naphthalene complex initiator according to a mass ratio of 2:1:0.04, heating to 60 β, stirring at 100rpm for reaction for 2 hours, adding ethylene glycol diglycidyl ether with the mass of 0.3 times of that of cyclohexene, continuing to react for 3 hours, terminating the reaction with ethanol, and finally drying in a vacuum drying oven to constant weight to obtain the epoxy polypentadiene; mixing terephthalic acid, ethylene glycol, isopropyl titanate and a dihydroxyl monomer containing a spiro structure according to a mass ratio of 1:1.3:0.04:0.25 in a nitrogen atmosphere, heating to 220 β, reacting for 3 hours, heating to 250 β, adjusting the pressure to 0.06MPa, adding epoxy polypentadiene with the mass of 0.2 times of that of terephthalic acid, continuing to react for 2 hours, heating to 270 β, continuing to react for 3 hours, discharging, and cooling to room temperature to obtain self-made PET; casting the self-made PET by an extruder, and stretching the self-made PET by a biaxial static stretcher at 92 β with a stretching ratio of 4.2 to obtain a self-made PET film, namely a base layer;
(2) Mixing an emulsifier A170 with deionized water according to a mass ratio of 1:15, uniformly stirring, adding octamethyl cyclotetrasiloxane with an 8-fold mass of the emulsifier A170, stirring for 50min at 2000rpm, heating to 80 β, continuously stirring for 3h, adding dibutyltin dilaurate with a 0.03-fold mass of the emulsifier A170 and aminosilane 602 with a 4-fold mass of the emulsifier A170, continuously reacting for 3h, cooling to 40 β, regulating the pH to 6.5 by using glacial acetic acid, and performing rotary evaporation to obtain amino hydroxyl silicone oil; mixing deionized water, sodium dodecyl sulfonate, styrene, butyl acrylate, polyoxyethylene octyl ether and amino hydroxyl silicone oil according to the mass ratio of 60:3:44:45:1:9, heating to 55 β, stirring at 100rpm for reaction, performing seed polymerization reaction after 30min, heating to 65 β, reacting for 30min, adding ammonium persulfate solution with the mass fraction of 3% which is 0.3 times of the mass of the amino hydroxyl silicone oil, heating to 70 β for reaction for 50min, heating to 75 β, reacting for 50min, cooling to 40 β, regulating the pH value to 7.8 by sodium hydroxide, and finally filtering by a 180-mesh screen to obtain modified styrene-acrylic emulsion; mixing the modified styrene-acrylic emulsion and a photoinitiator 184 according to a mass ratio of 8:1, and uniformly stirring to obtain a photocuring component;
(3) Mixing 4, 4-dicyclohexylmethane diisocyanate and polytetrahydrofuran according to a mass ratio of 13:50 under the nitrogen atmosphere, heating to 60 β, adding dibutyltin dilaurate with the mass of 0.004 times of that of polytetrahydrofuran after stirring uniformly, continuing to react for 5 hours, adding hydroxyethyl acrylate with the mass of 0.3 times of that of polytetrahydrofuran, heating to 70 β, and continuing to react for 4 hours to obtain a polyurethane acrylate oligomer, namely an ink component;
(4) Mixing the photo-curing component with the ink component according to the mass ratio to prepare the composite ink; uniformly coating composite ink on the surface of a base layer, wherein the coating amount is 0.3g/m 2 Ultraviolet curing is carried out at 60 β to obtain a colorful film; and finally, aluminizing the surface of the colorful film by using a vacuum aluminizing machine to obtain the weather-resistant deformation-resistant colorful film for the plate.
Example 2
(1) Mixing bisphenol A and methanesulfonic acid according to a mass ratio of 1.1:5, stirring for 3.5d at 150rpm, transferring into ice water, stirring uniformly, carrying out suction filtration, washing for 10 times with deionized water, and recrystallizing with 45% ethanol solution to obtain a dihydroxy monomer with a spiro structure; mixing naphthalene, sodium and tetrahydrofuran according to a mass ratio of 1:1:25 under a nitrogen atmosphere, and stirring until the mixture is black and green to prepare a naphthalene sodium complex initiator; mixing cyclohexene, isoprene and sodium naphthalene complex initiator according to a mass ratio of 2.5:1:0.06, heating to 70 β, stirring at 150rpm for reaction for 3 hours, adding ethylene glycol diglycidyl ether with the mass of 0.4 times of that of cyclohexene, continuing to react for 4 hours, terminating the reaction by using ethanol, and finally drying in a vacuum drying oven to constant weight to obtain epoxy polypentadiene; mixing terephthalic acid, ethylene glycol, isopropyl titanate and a dihydroxyl monomer containing a spiro structure according to a mass ratio of 1:1.4:0.05:0.3 in a nitrogen atmosphere, heating to 230 β, reacting for 4 hours, heating to 255 β, adjusting the pressure to 0.07MPa, adding epoxy polypentadiene with the mass of 0.3 times of that of terephthalic acid, continuing to react for 3 hours, heating to 275 β, continuing to react for 3.5 hours, discharging, and cooling to room temperature to obtain self-made PET; casting the self-made PET by an extruder, and stretching the self-made PET by a biaxial static stretcher at 94 β with a stretching ratio of 4.3 to obtain a self-made PET film, namely a base layer;
(2) Mixing an emulsifier A170 with deionized water according to a mass ratio of 1:17, uniformly stirring, adding octamethyl cyclotetrasiloxane with a mass ratio of 9 times that of the emulsifier A170, stirring for 60min at 3000rpm, heating to 82 β, continuously stirring for reaction for 4h, adding dibutyltin dilaurate with a mass ratio of 0.04 times that of the emulsifier A170 and aminosilane 602 with a mass ratio of 5 times that of the emulsifier A170, continuously reacting for 4.5h, cooling to 45 β, regulating pH to 6.7 by using glacial acetic acid, and performing rotary evaporation to obtain amino hydroxyl silicone oil; mixing deionized water, sodium dodecyl sulfonate, styrene, butyl acrylate, polyoxyethylene octyl ether and amino hydroxyl silicone oil according to the mass ratio of 70:3:44:45:1:10, heating to 56 β, stirring at 300rpm, performing seed polymerization reaction after 40min, heating to 66 β, reacting for 45min, adding ammonium persulfate solution with the mass fraction of 4% which is 0.45 times of the mass of the amino hydroxyl silicone oil, heating to 71 β for reacting for 70min, heating to 76 β for reacting for 70min, cooling to 42 β, regulating the pH value to 8.0 by sodium hydroxide, and finally filtering by a 180-mesh screen to obtain modified styrene-acrylic emulsion; mixing the modified styrene-acrylic emulsion and a photoinitiator 184 according to a mass ratio of 10:1, and uniformly stirring to obtain a photocuring component;
(3) Under the nitrogen atmosphere, mixing 4, 4-dicyclohexylmethane diisocyanate and polytetrahydrofuran according to the mass ratio of 14:50, heating to 61 β, adding dibutyltin dilaurate with the mass of 0.005 times of polytetrahydrofuran after stirring uniformly, continuing to react for 5.5 hours, adding hydroxyethyl acrylate with the mass of 0.35 times of polytetrahydrofuran, heating to 71 β, and continuing to react for 5 hours to obtain polyurethane acrylate oligomer, namely an ink component;
(4) Mixing the photo-curing component with the ink component according to the mass ratio to prepare the composite ink; uniformly coating composite ink on the surface of a base layer, wherein the coating amount is 0.4g/m 2 Ultraviolet curing is carried out at 65 β to obtain a colorful film; and finally, aluminizing the surface of the colorful film by using a vacuum aluminizing machine to obtain the weather-resistant deformation-resistant colorful film for the plate.
Example 3
(1) Mixing bisphenol A and methanesulfonic acid according to a mass ratio of 1.2:5, stirring for 4d at 200rpm, transferring into ice water, stirring uniformly, carrying out suction filtration, washing for 12 times with deionized water, and recrystallizing with 60% ethanol solution to obtain a dihydroxy monomer with a spiro structure; mixing naphthalene, sodium and tetrahydrofuran according to a mass ratio of 1:1:30 under a nitrogen atmosphere, and stirring until the mixture is black and green to prepare a naphthalene sodium complex initiator; mixing cyclohexene, isoprene and sodium naphthalene complex initiator according to a mass ratio of 3:1:0.08, heating to 80 β, stirring at 200rpm for reaction for 4 hours, adding ethylene glycol diglycidyl ether with the mass of 0.5 times of that of cyclohexene, continuing to react for 6 hours, terminating the reaction by using ethanol, and finally drying in a vacuum drying oven to constant weight to obtain the epoxy polypentadiene; mixing terephthalic acid, ethylene glycol, isopropyl titanate and a dihydroxyl monomer containing a spiro structure according to a mass ratio of 1:1.5:0.06:0.35 in a nitrogen atmosphere, heating to 240 β, reacting for 5 hours, heating to 260 β, adjusting the pressure to 0.08MPa, adding epoxy polypentadiene with the mass of 0.4 times of that of terephthalic acid, continuing to react for 4 hours, heating to 280 β, continuing to react for 4 hours, discharging, and cooling to room temperature to obtain self-made PET; casting the self-made PET by an extruder, and stretching the self-made PET by a biaxial static stretcher at 95 β with a stretching ratio of 4.4 to obtain a self-made PET film, namely a base layer;
(2) Mixing an emulsifier A170 with deionized water according to a mass ratio of 1:20, uniformly stirring, adding octamethyl cyclotetrasiloxane with a mass ratio of 10 times that of the emulsifier A170, stirring at 400rpm for 60min, heating to 85 β, continuously stirring for reaction for 6h, adding dibutyltin dilaurate with a mass ratio of 0.06 times that of the emulsifier A170 and aminosilane 602 with a mass ratio of 6 times that of the emulsifier A170, continuously reacting for 6h, cooling to 50 β, regulating pH to 6.8 by using glacial acetic acid, and performing rotary evaporation to obtain amino hydroxyl silicone oil; mixing deionized water, sodium dodecyl sulfonate, styrene, butyl acrylate, polyoxyethylene octyl ether and amino hydroxyl silicone oil according to the mass ratio of 80:3:44:45:1:11, heating to 58 β, stirring at 400rpm for reaction, carrying out seed polymerization reaction after 50min, heating to 68 β, reacting for 40min, adding ammonium persulfate solution with the mass fraction of 5% which is 0.6 times of the mass of the amino hydroxyl silicone oil, heating to 72 β for reaction for 90min, heating to 78 β for reaction for 90min, cooling to 45 β, regulating the pH value to 8.2 by sodium hydroxide, and finally filtering by a 180-mesh screen to obtain modified styrene-acrylic emulsion; mixing the modified styrene-acrylic emulsion and a photoinitiator 184 according to a mass ratio of 12:1, and uniformly stirring to obtain a photocuring component;
(3) Mixing 4, 4-dicyclohexylmethane diisocyanate and polytetrahydrofuran according to a mass ratio of 15:50 under the nitrogen atmosphere, heating to 62 β, stirring uniformly, adding dibutyltin dilaurate with the mass of 0.006 times that of polytetrahydrofuran, continuing to react for 6 hours, adding hydroxyethyl acrylate with the mass of 0.4 times that of polytetrahydrofuran, heating to 72 β, and continuing to react for 6 hours to obtain a polyurethane acrylate oligomer, namely an ink component;
(4) Mixing the photo-curing component with the ink component according to the mass ratio to prepare the composite ink; uniformly coating composite ink on the surface of a base layer, wherein the coating amount is 0.5g/m 2 Ultraviolet curing is carried out at 70 β to obtain a colorful film; and finally, aluminizing the surface of the colorful film by using a vacuum aluminizing machine to obtain the weather-resistant deformation-resistant colorful film for the plate.
Comparative example 1
Comparative example 1 has the same composition as example 2. The preparation method of the weather-resistant anti-deformation colorful film of the plate is different from that of the embodiment 2 in that the self-made PET film is prepared by adding epoxy polypentadiene into the prepared PET.
Comparative example 2
Comparative example 2 has the same composition as example 2. The preparation method of the weather-resistant anti-deformation colorful film of the plate is different from that of the embodiment 2 in that the self-made PET film is prepared by introducing a dihydroxy monomer containing a spiro structure into the prepared PET as a pre-modified monomer.
Comparative example 3
Comparative example 3 has the same composition as example 2. The preparation method of the weather-resistant anti-deformation colorful film of the plate is different from the example 2 only in that the light curing component comprises a photoinitiator and a styrene-acrylic emulsion.
Comparative example 4
Comparative example 4 has the same composition as example 2. The preparation method of the weather-resistant anti-deformation colorful film of the plate is different from that of the example 2 in that the ink component is polyurethane acrylic ester sold in the market.
Comparative example 5 has the same composition as example 2. The preparation method of the weather-resistant anti-deformation colorful film of the plate is different from that of the example 2 in that the photo-curing component comprises a photoinitiator and styrene-acrylic emulsion, and the ink component is polyurethane acrylate sold in the market.
Effect example
The following table 1 shows the results of performance analysis of weather-resistant anti-deformation glare films for panels prepared using examples 1 to 3 of the present invention and comparative examples 1 to 5:
TABLE 1
As is evident from comparison of the experimental data of examples in Table 1 with comparative examples, the weather resistance, deformation resistance and adhesion of the weather-resistant anti-deformation glare films of the sheets prepared by examples 1, 2 and 3 were good.
From the comparison of experimental data of the embodiment 1, the embodiment 2, the embodiment 3 and the comparative embodiment 1 and the comparative embodiment 2, it can be found that the preparation of PET introduces a dihydroxy monomer containing a spiro structure as a pre-modified monomer, and then adds a self-made PET film prepared from epoxy polypentadiene, and introduces the spiro structure into the PET structure, so that not only the rigidity structure on the PET molecular chain is increased, but also the weather resistance and the mechanical property are enhanced, the colorful film is prevented from being deformed by external force, a microporous structure can be formed in the PET, the adsorption effect is generated on the plate, and the cohesive force of the colorful film is enhanced; and then introducing epoxy polypentadiene to react with active groups on PET and dihydroxyl monomers to form a tighter cross-linked structure, so that the weather resistance of the colorful film is further enhanced.
From the experimental data comparison of example 1, example 2, example 3 and comparative example 3, comparative example 4 and comparative example 5, it can be found that the modified styrene-acrylic emulsion prepared by introducing amino hydroxyl silicone oil into the styrene-acrylic emulsion, and the urethane acrylate oligomer prepared by using polytetrahydrofuran as long carbon chain diol have higher flexibility and crosslinking density, and after being blended with the photo-curing component, the urethane acrylate oligomer can continuously react with the modified styrene-acrylic emulsion, and the styrene-acrylic emulsion with strong adhesive property is introduced into the UV coating, so that the adhesive force of the composite ink coating to the base layer and the vacuum aluminized layer is enhanced, and meanwhile, the mechanical property is enhanced, thereby enhancing the anti-deformation property of the colorful film.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The weather-resistant deformation-resistant colorful film for the plate is characterized by comprising a base layer, a UV coating and an aluminum layer; the base layer is a self-made PET film; the UV coating is a composite ink coating; the aluminum layer is a vacuum aluminum plating layer.
2. The weather-resistant anti-deformation colorful plate film according to claim 1, wherein the self-made PET film is prepared by introducing a dihydroxy monomer containing a spiro structure into PET to serve as a pre-modified monomer and adding epoxy polypentadiene.
3. The weather-resistant and deformation-resistant colorful sheet material film of claim 1, wherein the composite ink coating comprises a photo-curing component and an ink component; the light curing component comprises a photoinitiator and modified styrene-acrylic emulsion; the ink component is a urethane acrylate oligomer.
4. The weather-resistant anti-deformation colorful plate film according to claim 3, wherein the modified styrene-acrylic emulsion is prepared by introducing amino hydroxyl silicone oil into styrene-acrylic emulsion; the polyurethane acrylate oligomer is prepared by taking polytetrahydrofuran as long carbon chain diol.
5. The preparation method of the weather-resistant deformation-resistant colorful film for the plate is characterized by comprising the following specific steps of:
(1) Mixing terephthalic acid, ethylene glycol, isopropyl titanate and a dihydroxyl monomer containing a spiro structure according to a mass ratio of 1:1.3-1.5:0.04-0.06:0.25-0.35 in a nitrogen atmosphere, heating to 220-240 β, reacting for 3-5 h, heating to 250-260 β, adjusting the pressure to 0.06-0.08 MPa, adding epoxy polypentadiene with the mass of 0.2-0.4 times of that of terephthalic acid, continuously reacting for 2-4 h, heating to 270-280 β, continuously reacting for 3-4 h, discharging, and cooling to room temperature to obtain self-made PET; casting the self-made PET by an extruder, and stretching the self-made PET by a biaxial static stretcher at 92-95 β with a stretching ratio of 4.2-4.4 to obtain a self-made PET film, namely a base layer;
(2) Mixing deionized water, sodium dodecyl sulfonate, styrene, butyl acrylate, polyoxyethylene octyl ether and amino hydroxyl silicone oil according to the mass ratio of 60-80:3:44:45:1:9-11, heating to 55-58 β, stirring at 100-400 rpm for reaction, performing seed polymerization reaction after 30-50 min, heating to 65-68 β, reacting for 30-40 min, adding ammonium persulfate solution with the mass fraction of 3-5% and the mass fraction of 0.3-0.6 times that of the amino hydroxyl silicone oil, heating to 70-72 β for reaction for 50-90 min, heating to 75-78 β for reaction for 50-90 min, cooling to 40-45 β, regulating pH to 7.8-8.2 with sodium hydroxide, and finally filtering with a 180-mesh screen to obtain modified styrene-acrylic emulsion; mixing the modified styrene-acrylic emulsion and a photoinitiator 184 according to a mass ratio of 8-12:1, and uniformly stirring to obtain a photocuring component;
(3) Mixing 4, 4-dicyclohexylmethane diisocyanate and polytetrahydrofuran under the nitrogen atmosphere, heating to 60-62 β, uniformly stirring, adding dibutyltin dilaurate with the mass of 0.004-0.006 times that of polytetrahydrofuran, continuously reacting for 5-6 h, adding hydroxyethyl acrylate with the mass of 0.3-0.4 times that of polytetrahydrofuran, heating to 70-72 β, and continuously reacting for 4-6 h to obtain polyurethane acrylate oligomer, namely an ink component;
(4) Mixing the photo-curing component with the ink component to prepare a composite ink; uniformly coating composite ink on the surface of the base layer, wherein the coating amount is 0.3-0.5 g/m 2 Ultraviolet curing is carried out at 60-70 β to obtain a colorful film; and finally, aluminizing the surface of the colorful film by using a vacuum aluminizing machine to obtain the weather-resistant deformation-resistant colorful film for the plate.
6. The method for preparing the weather-resistant anti-deformation colorful film for the plate according to claim 5, wherein in the step (1): the preparation method of the dihydroxy monomer containing the spiro structure comprises the following steps: bisphenol A and methanesulfonic acid are mixed according to the mass ratio of 1-1.2:5, stirred for 3-4 d at 100-200 rpm, transferred into ice water, stirred uniformly, filtered by suction, washed for 8-12 times by deionized water, and recrystallized by ethanol solution with the mass fraction of 30-60%, thus obtaining the dihydroxy monomer with the spiro structure.
7. The method for preparing the weather-resistant anti-deformation colorful film for the plate according to claim 5, wherein in the step (1): the preparation method of the epoxy polypentadiene comprises the following steps: mixing naphthalene, sodium and tetrahydrofuran according to a mass ratio of 1:1:20-30 in a nitrogen atmosphere, and stirring until the mixture is black and green to prepare a naphthalene sodium complex initiator; mixing cyclohexene, isoprene and sodium naphthalene complex initiator according to the mass ratio of 2-3:1:0.04-0.08, heating to 60-80 β, stirring at 100-200 rpm for reaction for 2-4 h, adding ethylene glycol diglycidyl ether with the mass of 0.3-0.5 times of cyclohexene, continuing to react for 3-6 h, terminating the reaction with ethanol, and finally drying in a vacuum drying oven to constant weight to obtain the epoxy polypentadiene.
8. The method for preparing the weather-resistant anti-deformation colorful film for the plate according to claim 5, wherein in the step (2): the preparation method of the amino hydroxyl silicone oil comprises the following steps: mixing the emulsifier A170 with deionized water according to the mass ratio of 1:15-20, stirring uniformly, adding octamethyl cyclotetrasiloxane with the mass ratio of 8-10 times that of the emulsifier A170, stirring at 2000-4000 rpm for 40-60 min, heating to 80-85 β, continuing stirring for reacting for 3-6 h, adding dibutyltin dilaurate with the mass ratio of 0.03-0.06 times that of the emulsifier A170 and aminosilane 602 with the mass ratio of 4-6 times that of the emulsifier A170, continuing reacting for 3-6 h, cooling to 40-50 β, regulating the pH to 6.5-6.8 by using glacial acetic acid, and performing rotary evaporation to obtain the amino hydroxyl silicone oil.
9. The method for preparing the weather-resistant anti-deformation colorful film for the plate according to claim 5, wherein in the step (3): the mass ratio of the 4, 4-dicyclohexylmethane diisocyanate to the polytetrahydrofuran is 13-15:50.
10. The method for preparing the weather-resistant anti-deformation colorful film for the plate according to claim 5, wherein in the step (4): the mass ratio of the photo-curing component to the ink component is 1:18-25.
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