CN116769413B - Anti-fouling TPU high-low temperature film and preparation method thereof - Google Patents
Anti-fouling TPU high-low temperature film and preparation method thereof Download PDFInfo
- Publication number
- CN116769413B CN116769413B CN202310766959.5A CN202310766959A CN116769413B CN 116769413 B CN116769413 B CN 116769413B CN 202310766959 A CN202310766959 A CN 202310766959A CN 116769413 B CN116769413 B CN 116769413B
- Authority
- CN
- China
- Prior art keywords
- fouling
- layer
- low temperature
- tpu
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010410 layer Substances 0.000 claims abstract description 137
- 239000011248 coating agent Substances 0.000 claims abstract description 67
- 238000000576 coating method Methods 0.000 claims abstract description 67
- 239000012790 adhesive layer Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 229920002799 BoPET Polymers 0.000 claims abstract description 17
- 239000003973 paint Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 73
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 43
- 239000003822 epoxy resin Substances 0.000 claims description 37
- 229920000647 polyepoxide Polymers 0.000 claims description 37
- 239000002105 nanoparticle Substances 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 24
- 229920005749 polyurethane resin Polymers 0.000 claims description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims description 24
- 239000003381 stabilizer Substances 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000009210 therapy by ultrasound Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 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 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 230000002209 hydrophobic effect Effects 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 7
- 239000000413 hydrolysate Substances 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- 239000004831 Hot glue Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 abstract description 95
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 95
- 238000009776 industrial production Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 230000000007 visual effect Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 49
- 239000000047 product Substances 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- -1 phenolic amine Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- DXODQEHVNYHGGW-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DXODQEHVNYHGGW-UHFFFAOYSA-N 0.000 description 2
- VBGGLSWSRVDWHB-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBGGLSWSRVDWHB-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only 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
- 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
-
- 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
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of TPU (thermoplastic polyurethane), in particular to an anti-fouling TPU high-low temperature film and a preparation method thereof. The anti-fouling TPU high-low temperature film comprises a PET film layer, a release layer, an anti-fouling film layer, a pattern layer, a second adhesive layer, a TPU substrate layer, a first adhesive layer and a release film layer from top to bottom, wherein the anti-fouling film layer is formed by coating transparent amphiphobic paint. The anti-fouling TPU high-low temperature film provided by the invention has good anti-fouling performance, visual effect and wear resistance on the basis of inheriting the excellent performances of good expansion and reduction performance, portability and fine touch of the TPU high-low temperature film. The preparation method of the anti-fouling TPU high-low temperature film has the advantages of simple processing technology, good industrial production applicability and stable product quality, and the prepared anti-fouling TPU high-low temperature film has excellent comprehensive performance and can meet the requirements of industrial production and users.
Description
Technical Field
The invention relates to the technical field of TPU (thermoplastic polyurethane), in particular to an anti-fouling TPU high-low temperature film and a preparation method thereof.
Background
Thermoplastic polyurethane (Thermoplastic Polyurethane, TPU for short) is a high molecular material with excellent performances of wear resistance, oil resistance, transparency, good elasticity and the like, and can be applied to various industrial and civil fields. Furthermore, the TPU high-low temperature film is formed by compounding TPU at high temperature and low temperature by using a compounding process, has excellent physical properties and is widely applied to shoe materials, clothing, sports goods, water supplies and the like. The prior art of TPU high-low temperature films mainly focuses on the compounding process direction of the TPU high-low temperature films and cloth materials and the performance directions of the TPU high-low temperature films such as water resistance, ventilation, aging resistance and the like. Namely, when the conventional TPU high-low temperature film is used for the product, the antifouling performance cannot be well considered, so that stains are easy to be stained on the surface of the product, and the aesthetic property and the practicability of the product are affected. Therefore, the performance of the TPU high-low temperature film with wide application range is further improved, and the TPU high-low temperature film has important significance for the industrial and civil fields.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the anti-fouling TPU high-low temperature film, which is coated by the transparent amphiphobic coating to form an anti-fouling film layer, so that the anti-fouling film layer and other film layers are mutually attached to form a whole, and when the anti-fouling TPU high-low temperature film is applied to products such as shoe materials, clothes and the like, the surface of the product has anti-fouling performance, the effect of water and oil repellency can be achieved, stains are prevented from adhering to the surface, the protection effect is achieved on the product, and the attractiveness and the practicability of the product are considered.
The invention further aims to provide a preparation method of the anti-fouling TPU high-low temperature film, which has the advantages of simple processing technology, good industrial production applicability and stable product quality, and the prepared anti-fouling TPU high-low temperature film has excellent anti-fouling performance, visual effect and wear resistance on the basis of inheriting the excellent performances of good expansion and reduction performance, portability and fine touch of the TPU high-low temperature film, and can meet the requirements of markets on the TPU high-low temperature film.
The aim of the invention is achieved by the following technical scheme: an anti-fouling TPU high-low temperature film comprises a PET film layer, a release layer, an anti-fouling film layer, a pattern layer, a second adhesive layer, a TPU substrate layer, a first adhesive layer and a release film layer from top to bottom; the anti-fouling film layer is a transparent amphiphobic film layer, and the transparent amphiphobic film layer is formed by coating transparent amphiphobic paint.
The anti-fouling TPU high-low temperature film has good anti-fouling performance by arranging the anti-fouling film layer, can play a role of hydrophobic and oleophobic, and can prevent stains from polluting the surface of a product, meanwhile, the anti-fouling film layer is a transparent film layer, so that a pattern layer on the lower surface of the anti-fouling TPU high-low temperature film can be clearly presented, and the PET film layer, the release layer and the release film layer can be removed when the anti-fouling TPU high-low temperature film is used, and the anti-fouling TPU high-low temperature film is attached to products such as shoe materials, clothing and the like through the first adhesive layer; the anti-fouling TPU high-low temperature film has the advantages of simple structure, attractive appearance, good anti-fouling performance, convenience in use and strong practicability, and can provide good experience for users.
In the above technical scheme, the first adhesive layer is a TPU adhesive layer. The first adhesive layer can be used for firmly adhering the anti-fouling TPU high-low temperature film to the surfaces of products such as bearing shoe materials, clothes and the like.
In the above technical scheme, the second adhesive layer is an ABS adhesive layer, a PE adhesive layer or a PP adhesive layer. The pattern layer can be adhered to the TPU substrate layer by adopting the second adhesive layer, so that the TPU substrate layer has firm adhesive force.
In the technical scheme, the transparent amphiphobic coating comprises the following raw materials in parts by weight: 5-10 parts of silicon dioxide nano particles, 8-15 parts of silane coupling agent, 4-14 parts of epoxy resin, 7-12 parts of polyurethane resin, 15-40 parts of dispersing agent, 20-45 parts of stabilizer, 0.5-1.0 part of regulator, 2-10 parts of curing agent and 10-30 parts of deionized water.
In the technical scheme, the preparation method of the transparent amphiphobic coating comprises the following steps of:
(1) Adding the silicon dioxide nano particles into a dispersing agent, uniformly mixing, and carrying out ultrasonic treatment for 10-40min to obtain a solution A;
(2) Mixing deionized water and a stabilizer, stirring uniformly, adding a regulator, regulating the pH value to be 2-5 to obtain a solution B, adding a silane coupling agent into the solution B, and pre-hydrolyzing for 30-60min to obtain a silane coupling agent hydrolysate;
(3) Mixing the solution A with the silane coupling agent hydrolysate, and stirring for 2-5 hours at 45-75 ℃ in a magnetic stirrer to obtain a solution C;
(4) Adding polyurethane resin into the solution C, performing ultrasonic treatment for 10-30min, and stirring for 5-20min by using a magnetic stirrer to obtain a solution D;
(5) Adding the epoxy resin and the curing agent into the solution D, mixing, and carrying out ultrasonic treatment for 20-60min to obtain the transparent amphiphobic coating.
In the above technical solution, the silica nanoparticles are hydrophobic silica nanoparticles.
In the above technical scheme, the dispersing agent is at least one of toluene, xylene, acetic acid or ethyl acetate. Preferably, the dispersing agent is a mixed solution of xylene and ethyl acetate. More preferably, the volume ratio of xylene to ethyl acetate is 1-3:1.
The silicon dioxide nano particles adopted in the invention can enable the transparent amphiphobic coating to have a rough surface when the anti-fouling film layer is constructed, so that water stains and oil stains are prevented from easily infiltrating the surface of a product, and further the residual stains are avoided. Meanwhile, the dispersing agent and the silicon dioxide nano particles are mixed, so that the dispersion of the silicon dioxide nano particles in a coating system can be promoted, the particle agglomeration phenomenon of the silicon dioxide nano particles is avoided, and the wettability of the anti-fouling film layer is further influenced. Furthermore, the invention controls the dosage of the dispersing agent, thereby avoiding the contact angle of the anti-fouling film layer from being reduced due to too little or too much dispersing agent, and negatively affecting the hydrophobic and oleophobic performance of the anti-fouling film layer.
In the technical scheme, the silane coupling agent is a fluorine-containing silane coupling agent. Preferably, the fluorine-containing silane coupling agent is at least one of perfluorodecyl trimethoxy silane, perfluorodecyl triethoxy silane, perfluorooctyl trimethoxy silane or perfluorooctyl triethoxy silane.
In the above technical solution, the stabilizer is at least one of methanol or ethanol.
In the above technical scheme, the regulator is at least one of formic acid, acetic acid, hydrochloric acid or sulfuric acid. Preferably, the regulator is a mixed solution of acetic acid and hydrochloric acid. More preferably, the mass ratio of the hydrochloric acid to the acetic acid is 1:13-17.
According to the invention, the fluorine-containing silane is adopted to modify the silicon dioxide nano particles, so that the surface composition structure of the silicon dioxide nano particles can be effectively regulated, the silicon dioxide nano particles have a rough structure and simultaneously have the characteristic of low surface free energy, and further the anti-fouling film layer has good hydrophobic and oleophobic properties. Furthermore, before the modification treatment of the silica nanoparticles, the fluorosilane needs to be hydrolyzed, so that hydroxyl groups on the surfaces of the silica nanoparticles and the fluorosilane can be condensed to form silicon-oxygen bonds, the polarity of the surfaces of the silica nanoparticles is weakened, and the effect of the fluorosilane is avoided from being unable to be exerted. After the regulator adopted in the invention is added, the hydrolysis of the silane coupling agent can be promoted, and the production process is accelerated.
In the technical scheme, the epoxy resin is bisphenol A type epoxy resin. Preferably, the bisphenol A type epoxy resin is at least one of E-51, E-54, NPEL-127 or NPEL-128.
In the above technical scheme, the curing agent is a phenolic amine curing agent. Preferably, the phenolic amine curative is at least one of TZ-500, TZ-550 or TZ-600.
The bisphenol A epoxy resin used in the invention has excellent physical and mechanical properties and adhesive properties, and the bisphenol A epoxy resin and polyurethane resin are compounded for use, so that the transparent amphiphobic coating can integrate the advantages of the bisphenol A epoxy resin and the polyurethane resin, and has flexibility and durability on the basis of the characteristics of the epoxy resin. Furthermore, the epoxy resin also has thermosetting property, can form a cured product with excellent performance with a curing agent, has excellent chemical stability, and meets the requirement of sustainable use of products.
According to the invention, the raw materials and the preparation method are adopted to prepare the transparent amphiphobic coating, so that the raw materials interact with each other, the silica nanoparticles modified by the silane coupling agent enable the anti-fouling film layer coated by the transparent amphiphobic coating to have the basis of roughness and low surface energy, the polyurethane resin and the epoxy resin are used in a composite manner, and the modified silica nanoparticles can effectively fill the pore canal in the composite resin, so that the film forming performance, the anti-fouling performance, the adhesion performance and the durability of the transparent amphiphobic coating can be further improved; the addition of the dispersing agent, the stabilizing agent, the regulator, the curing agent and the deionized water can bring the performance of the raw materials into play to the maximum, the raw materials of the transparent amphiphobic coating complement each other, and the transparent amphiphobic coating can be formed into a film by using a coating mode to form an anti-fouling film when in use, so that the anti-fouling film has good hydrophobic and oleophobic performance and good light transmittance. In addition, the method strictly controls the parameters of the treatment temperature, time or pH value of each step in the preparation method of the transparent amphiphobic coating, and avoids the condition that the mixing of the raw materials is insufficient due to the too low parameters or the performance is reduced due to the too high reaction of the raw materials, thereby influencing the quality of the finally prepared transparent amphiphobic coating.
The invention also provides a preparation method of the anti-fouling TPU high-low temperature film, which comprises the following steps:
(S1) taking a TPU substrate layer, coating hot melt adhesive on the lower surface of the TPU substrate layer, drying to form a first adhesive layer, and attaching a release film on the lower surface of the first adhesive layer to form a release film layer;
(S2) taking a PET film layer, coating a release layer coating on the upper surface of the PET film layer, drying to form a release layer, coating a transparent amphiphobic coating on the upper surface of the release layer, drying to form an anti-fouling film layer, and printing on the upper surface of the anti-fouling film layer to form a pattern layer;
and (S3) coating a hot melt adhesive on the upper surface of the TPU substrate layer, drying to form a second adhesive layer, attaching the pattern layer on the upper surface of the second adhesive layer, and drying to obtain the anti-fouling TPU high-low temperature film.
The preparation method of the anti-fouling TPU high-low temperature film has the advantages of simple processing technology, good industrial production applicability and stable product quality, and the prepared anti-fouling TPU high-low temperature film has good hydrophobic and oleophobic properties, visual effects and wear resistance, and can meet the demands of markets on TPU high-low temperature films.
The invention has the beneficial effects that: the anti-fouling TPU high-low temperature film is sequentially provided with a PET film layer, a release layer, an anti-fouling film layer, a pattern layer, a second adhesive layer, a TPU substrate layer, a first adhesive layer and a release film layer from top to bottom, wherein the pattern layer is a 3D pattern layer and can be set into different patterns according to requirements; the anti-fouling film layer is a transparent amphiphobic film layer formed by coating a transparent amphiphobic coating, has the advantages of good hydrophobic and oleophobic properties, can prevent stains from being stained on the surface, and has transparency, so that a pattern layer on the lower surface of the anti-fouling film layer is presented, and the surface of a product has good visual effect.
The transparent amphiphobic coating is prepared by modifying silicon dioxide nano particles by using a silane coupling agent, so that an anti-fouling film layer coated by the transparent amphiphobic coating has roughness and low surface energy, and water stains or oil stains have a contact angle which cannot be infiltrated on the surface of the anti-fouling film layer so as to achieve the effects of water repellency and oil repellency; in addition, the film forming performance, the adhesion performance and the wear resistance of the anti-fouling film layer are further improved by the composite resin of the epoxy resin and the polyurethane resin, so that the anti-fouling film layer can be firmly connected with the pattern layer, and the anti-fouling performance can be ensured not to be influenced by external friction during use.
The preparation method of the anti-fouling TPU high-low temperature film has the advantages of simple processing technology, good industrial production applicability and high production efficiency, and the prepared anti-fouling TPU high-low temperature film can be widely applied to the surfaces of products such as shoe materials, clothes and the like, so that the anti-fouling TPU high-low temperature film has good anti-fouling property and wear resistance while taking the aesthetic property of the products into consideration, and is favorable for meeting the demands of users.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
Example 1
In the embodiment, the anti-fouling TPU high-low temperature film comprises a PET film layer, a release layer, an anti-fouling film layer, a pattern layer, a second adhesive layer, a TPU substrate layer, a first adhesive layer and a release film layer from top to bottom; the anti-fouling film layer is a transparent amphiphobic film layer, and the transparent amphiphobic film layer is formed by coating transparent amphiphobic paint.
The anti-fouling TPU high-low temperature film has good anti-fouling performance by arranging the anti-fouling film layer, can play a role of hydrophobic and oleophobic, and can prevent stains from polluting the surface of a product, meanwhile, the anti-fouling film layer is a transparent film layer, so that a pattern layer on the lower surface of the anti-fouling TPU high-low temperature film can be clearly presented, and the PET film layer, the release layer and the release film layer can be removed when the anti-fouling TPU high-low temperature film is used, and the anti-fouling TPU high-low temperature film is attached to products such as shoe materials, clothes and the like through the adhesive layer; the anti-fouling TPU high-low temperature film has the advantages of simple structure, attractive appearance, good anti-fouling performance, convenience in use and strong practicability, and can provide good experience for users.
Further, the thickness of the PET film layer is 50-75 mu m.
Further, the thickness of the release layer is 15-40 μm.
Further, the thickness of the anti-fouling film layer is 3-7 mu m.
Further, the thickness of the second adhesive layer is 10-20 μm.
Further, the thickness of the TPU substrate layer is 75-125 μm.
Further, the thickness of the first adhesive layer is 5-30 μm.
Further, the thickness of the release film layer is 50-100 mu m.
Further, the first adhesive layer is a TPU adhesive layer. The first adhesive layer can be used for firmly adhering the anti-fouling TPU high-low temperature film to the surface of a bearing product.
Further, the second adhesive layer is an ABS adhesive layer, a PE adhesive layer or a PP adhesive layer. The pattern layer can be adhered to the TPU substrate layer by adopting the second adhesive layer to obtain firm adhesive force.
Example 2
In this embodiment, the transparent amphiphobic coating comprises the following raw materials in parts by weight: 7 parts of silicon dioxide nano particles, 12 parts of silane coupling agent, 9 parts of epoxy resin, 9 parts of polyurethane resin, 25 parts of dispersing agent, 35 parts of stabilizer, 0.8 part of regulator, 5 parts of curing agent and 20 parts of deionized water.
In this embodiment, the preparation method of the transparent amphiphobic coating includes the following steps:
(1) Adding the silicon dioxide nano particles into a dispersing agent, uniformly mixing, and carrying out ultrasonic treatment for 25min to obtain a solution A;
(2) Mixing deionized water and a stabilizer, stirring uniformly, adding a regulator, regulating the pH value to be 3 to obtain a solution B, adding a silane coupling agent into the solution B, and pre-hydrolyzing for 40min to obtain a silane coupling agent hydrolysate;
(3) Mixing the solution A with the silane coupling agent hydrolysate, and stirring for 3 hours at 60 ℃ in a magnetic stirrer to obtain a solution C;
(4) Adding polyurethane resin into the solution C, performing ultrasonic treatment for 15min, and stirring for 10min by using a magnetic stirrer to obtain a solution D;
(5) And adding the epoxy resin and the curing agent into the solution D, mixing, and carrying out ultrasonic treatment for 30min to obtain the transparent amphiphobic coating.
In this embodiment, the silica nanoparticles are hydrophobic silica nanoparticles.
In this embodiment, the dispersing agent is a mixed solution of xylene and ethyl acetate in a volume ratio of 2:1.
In this embodiment, the silane coupling agent is perfluorodecyl trimethoxy silane.
In this embodiment, the stabilizer is methanol.
In this embodiment, the regulator is a mixed solution of hydrochloric acid and acetic acid in a mass ratio of 1:15.
In this embodiment, the epoxy resin is bisphenol A type epoxy resin E-51.
In this embodiment, the curing agent is a phenolic amine curing agent TZ-500.
In this example, the hydrophobic silica nanoparticle was a hydrophobic silica having a model R974 from demarcate corporation, and the polyurethane resin was a polyurethane resin having a model 3070A from bayer, germany.
The embodiment also provides a preparation method of the anti-fouling TPU high-low temperature film, which comprises the following steps:
(S1) taking a TPU substrate layer, coating hot melt adhesive on the lower surface of the TPU substrate layer, drying to form a first adhesive layer, and attaching a release film on the lower surface of the first adhesive layer to form a release film layer;
(S2) taking a PET film layer, coating a release layer coating on the upper surface of the PET film layer, drying to form a release layer, coating a transparent amphiphobic coating on the upper surface of the release layer, drying to form an anti-fouling film layer, and printing on the upper surface of the anti-fouling film layer to form a pattern layer;
and (S3) coating a hot melt adhesive on the upper surface of the TPU substrate layer, drying to form a second adhesive layer, attaching the pattern layer on the upper surface of the second adhesive layer, and drying to obtain the anti-fouling TPU high-low temperature film.
The remainder of this example is the same as example 1.
Example 3
In this embodiment, the transparent amphiphobic coating comprises the following raw materials in parts by weight: 5 parts of silicon dioxide nano particles, 9 parts of silane coupling agent, 7 parts of epoxy resin, 7 parts of polyurethane resin, 25 parts of dispersing agent, 35 parts of stabilizer, 0.8 part of regulator, 4 parts of curing agent and 20 parts of deionized water.
In this embodiment, the silane coupling agent is perfluorodecyl triethoxysilane.
In this embodiment, the stabilizer is ethanol.
In this embodiment, the epoxy resin is bisphenol A type epoxy resin NPEL-128.
In this embodiment, the curing agent is an aldehyde amine curing agent TZ-550.
The remainder of this embodiment is the same as that of embodiment 2.
Example 4
In this embodiment, the transparent amphiphobic coating comprises the following raw materials in parts by weight: 9 parts of silicon dioxide nano particles, 14 parts of silane coupling agent, 10 parts of epoxy resin, 10 parts of polyurethane resin, 25 parts of dispersing agent, 35 parts of stabilizer, 0.8 part of regulator, 5.5 parts of curing agent and 20 parts of deionized water.
In this embodiment, the silane coupling agent is perfluorodecyl triethoxysilane.
In this embodiment, the stabilizer is ethanol.
In this embodiment, the epoxy resin is bisphenol A type epoxy resin E-54.
In this example, the curing agent is phenolic amine curing agent TZ-550.
The remainder of this embodiment is the same as that of embodiment 2.
Example 5
In this embodiment, the transparent amphiphobic coating comprises the following raw materials in parts by weight: 7 parts of silicon dioxide nano particles, 12 parts of silane coupling agent, 9 parts of epoxy resin, 9 parts of polyurethane resin, 15 parts of dispersing agent, 25 parts of stabilizer, 0.6 part of regulator, 5 parts of curing agent and 15 parts of deionized water.
In this embodiment, the silane coupling agent is perfluorodecyl triethoxysilane.
In this embodiment, the stabilizer is ethanol.
In this embodiment, the epoxy resin is bisphenol A type epoxy resin NPEL-127.
In this embodiment, the curing agent is a phenolic amine curing agent TZ-600.
The remainder of this embodiment is the same as that of embodiment 2.
Example 6
In this embodiment, the transparent amphiphobic coating comprises the following raw materials in parts by weight: 7 parts of silicon dioxide nano particles, 12 parts of silane coupling agent, 9 parts of epoxy resin, 9 parts of polyurethane resin, 35 parts of dispersing agent, 45 parts of stabilizer, 1.0 part of regulator, 5 parts of curing agent and 30 parts of deionized water.
In this embodiment, the silane coupling agent is perfluorooctyl trimethoxy silane.
In this embodiment, the stabilizer is methanol.
In this embodiment, the epoxy resin is bisphenol A type epoxy resin NPEL-127.
In this example, the curing agent is phenolic amine curing agent TZ-550.
The remainder of this embodiment is the same as that of embodiment 2.
Example 7
In this embodiment, the preparation method of the transparent amphiphobic coating includes the following steps:
(1) Adding the silicon dioxide nano particles into a dispersing agent, uniformly mixing, and carrying out ultrasonic treatment for 15min to obtain a solution A;
(2) Mixing deionized water and a stabilizer, stirring uniformly, adding a regulator, regulating the pH value to be 3 to obtain a solution B, adding a silane coupling agent into the solution B, and pre-hydrolyzing for 30min to obtain a silane coupling agent hydrolysate;
(3) Mixing the solution A with the silane coupling agent hydrolysate, and stirring for 4 hours at 50 ℃ in a magnetic stirrer to obtain a solution C;
(4) Adding polyurethane resin into the solution C, performing ultrasonic treatment for 12min, and stirring for 5min by using a magnetic stirrer to obtain a solution D;
(5) And adding the epoxy resin and the curing agent into the solution D, mixing, and carrying out ultrasonic treatment for 20min to obtain the transparent amphiphobic coating.
The remainder of this embodiment is the same as that of embodiment 2.
Example 8
In this embodiment, the preparation method of the transparent amphiphobic coating includes the following steps:
(1) Adding the silicon dioxide nano particles into a dispersing agent, uniformly mixing, and carrying out ultrasonic treatment for 38min to obtain a solution A;
(2) Mixing deionized water and a stabilizer, stirring uniformly, adding a regulator, regulating the pH value to be 3 to obtain a solution B, adding a silane coupling agent into the solution B, and pre-hydrolyzing for 55min to obtain a silane coupling agent hydrolysate;
(3) Mixing the solution A with the silane coupling agent hydrolysate, and stirring for 2 hours at 65 ℃ in a magnetic stirrer to obtain a solution C;
(4) Adding polyurethane resin into the solution C, performing ultrasonic treatment for 20min, and stirring for 15min by using a magnetic stirrer to obtain a solution D;
(5) And adding the epoxy resin and the curing agent into the solution D, mixing, and carrying out ultrasonic treatment for 45min to obtain the transparent amphiphobic coating.
The remainder of this embodiment is the same as that of embodiment 2.
Comparative example 1
This comparative example is different from example 2 in that the transparent amphiphobic coating is prepared by replacing epoxy resin with an equal amount of polyurethane resin and no curing agent is added, and the corresponding preparation methods are different.
Namely, in the comparative example, the transparent amphiphobic coating comprises the following raw materials in parts by weight: 7 parts of silicon dioxide nano particles, 12 parts of silane coupling agent, 18 parts of polyurethane resin, 25 parts of dispersing agent, 35 parts of stabilizer, 0.8 part of regulator and 20 parts of deionized water.
In this embodiment, the preparation method of the transparent amphiphobic coating includes the following steps:
(1) Adding the silicon dioxide nano particles into a dispersing agent, uniformly mixing, and carrying out ultrasonic treatment for 25min to obtain a solution A;
(2) Mixing deionized water and a stabilizer, stirring uniformly, adding a regulator, regulating the pH value to be 3 to obtain a solution B, adding a silane coupling agent into the solution B, and pre-hydrolyzing for 40min to obtain a silane coupling agent hydrolysate;
(3) Mixing the solution A with the silane coupling agent hydrolysate, and stirring for 3 hours at 60 ℃ in a magnetic stirrer to obtain a solution C;
(4) Adding polyurethane resin into the solution C, carrying out ultrasonic treatment for 30min, and stirring for 20min by using a magnetic stirrer to obtain the transparent amphiphobic coating.
The remainder of this embodiment is the same as that of embodiment 2.
Comparative example 2
This comparative example differs from example 2 in that the transparent amphiphobic coating is replaced with an equal amount of epoxy resin instead of polyurethane resin, and the corresponding preparation methods are different.
Namely, in the comparative example, the transparent amphiphobic coating comprises the following raw materials in parts by weight: 7 parts of silicon dioxide nano particles, 12 parts of silane coupling agent, 18 parts of epoxy resin, 25 parts of dispersing agent, 35 parts of stabilizer, 0.8 part of regulator, 10 parts of curing agent and 20 parts of deionized water.
In this embodiment, the preparation method of the transparent amphiphobic coating includes the following steps:
(1) Adding the silicon dioxide nano particles into a dispersing agent, uniformly mixing, and carrying out ultrasonic treatment for 25min to obtain a solution A;
(2) Mixing deionized water and a stabilizer, stirring uniformly, adding a regulator, regulating the pH value to be 3 to obtain a solution B, adding a silane coupling agent into the solution B, and pre-hydrolyzing for 40min to obtain a silane coupling agent hydrolysate;
(3) Mixing the solution A with the silane coupling agent hydrolysate, and stirring for 3 hours at 60 ℃ in a magnetic stirrer to obtain a solution C;
(4) And adding the epoxy resin and the curing agent into the solution C, mixing, and carrying out ultrasonic treatment for 45min to obtain the transparent amphiphobic coating.
The remainder of this embodiment is the same as that of embodiment 2.
Performance test
The thickness of the PET film layer of the anti-fouling TPU high-low temperature films prepared in examples 2-8 and comparative examples 1-2 was controlled to be 50 μm, the thickness of the release layer was controlled to be 20 μm, the thickness of the anti-fouling film layer was controlled to be 5 μm, the thickness of the second adhesive layer was controlled to be 15 μm, the thickness of the TPU substrate layer was controlled to be 75 μm, the thickness of the first adhesive layer was controlled to be 10 μm, the thickness of the release film layer was controlled to be 50 μm, and the second adhesive layer was controlled to be PE adhesive layer, and performance test was performed on the prepared anti-fouling TPU high-low temperature films. The wettability, wear resistance, transmittance and chemical stability of the anti-fouling TPU high-low temperature film after tearing off the PET film layer and the release layer are tested, the adhesion between the anti-fouling film layer and the pattern layer is tested under different conditions, and the test data are shown in the following table 1:
table 1: performance test Table for the fouling resistant TPU high and low temperature films prepared in examples 2-8 and comparative examples 1-2
The wettability test is to lay the side of the anti-fouling TPU high-low temperature film close to the anti-fouling film layer on a contact angle measuring instrument platform, and then drop 5 microliters of water or oil on the surface in sequence to measure the contact angle.
The transmittance test is to measure the antifouling TPU high and low temperature film by using an ultraviolet-visible spectrophotometer, and the range is 200-800nm.
The abrasion resistance test adopts a test method of relative sliding with sand paper to detect the abrasion resistance of the anti-pollution TPU high and low temperature film, and specifically comprises the steps of buckling one side of the anti-pollution TPU high and low temperature film close to an anti-pollution film layer on the surface of the sand paper, pressing the anti-pollution TPU high and low temperature film on the film with a weight with a certain weight, pulling the anti-pollution TPU high and low temperature film by 10 cm with fixed pulling force, rotating the film 180 degrees clockwise, and pulling the film by 10 cm again, wherein the forward pulling and the reverse pulling are 1 abrasion cycle. After abrasion was completed, the film was removed for contact angle measurement.
The chemical stability test is to soak the anti-fouling TPU high and low temperature film in hydrochloric acid solution (pH=2), sodium hydroxide solution (pH=14) and 3.5wt% NaCl solution respectively, take out the contact angle of the measurement film after two hours, divide the stability degree into 1-5 grades according to the change degree of the contact angle, stabilize grade 1, and gradually decrease the stability degree of grade 2-5.
The adhesion test adopts ISO2409, the adhesion degree is classified into 0-5 grades, the 0 grade is good in adhesion, and the adhesion degree of 1-5 grades is gradually reduced.
As can be seen from the data in the table, the anti-fouling TPU high-low temperature film prepared in the embodiment 2 of the invention has excellent anti-fouling property and wear resistance, and has good light transmittance, so that the pattern layer in the anti-fouling TPU high-low temperature film is presented, and the overall aesthetic property of the product is ensured. The anti-fouling TPU high and low temperature films prepared in the comparative examples 2 to 6 can show that the interaction between the raw materials is affected when the ratio of the raw materials contained in the transparent amphiphobic coating is insufficient or excessive, and in addition, the preparation method of the transparent amphiphobic coating can also have an effect on the anti-fouling TPU high and low temperature films when the ultrasonic time or the stirring time is insufficient or too long or the stirring temperature is too low or too high, and the dispersion degree of the raw materials in the system and the bonding degree between the raw materials can be affected. The experimental data of examples 2-8 show that the raw material ratio of the transparent amphiphobic coating and the preparation method thereof have an influence on the performance of the anti-fouling TPU high and low temperature film, specifically, when the operation parameters of the raw material ratio and the preparation method thereof are not suitable, the contact angles of water and oil before and after abrasion of the anti-fouling TPU high and low temperature film are reduced, the abrasion degree is different, and the hydrophobicity, oleophobicity and abrasion resistance of the anti-fouling TPU high and low temperature film are negatively influenced.
Meanwhile, as is clear from the comparison between the example 2 and the comparative examples 1-2, the chemical stability of the anti-fouling TPU high-low temperature film is poor without adding epoxy resin, the adhesion between the anti-fouling film layer and the pattern layer is insufficient, and the wettability of the anti-fouling TPU high-low temperature film is weak and the abrasion degree is serious without adding polyurethane resin. Therefore, the transparent amphiphobic coating formed by interaction of the epoxy resin and the polyurethane resin and other raw materials is matched with the application mode of coating, and meanwhile, the preparation method of the anti-fouling TPU high-low temperature film is combined, and the prepared anti-fouling TPU high-low temperature film has the characteristics of good hydrophobicity, oleophobicity, wear resistance, film forming, stability and attractive appearance.
The preparation method of the anti-fouling TPU high-low temperature film has the advantages of simple processing technology, good industrial production applicability and high production speed, and the prepared anti-fouling TPU high-low temperature film can be widely applied to the surfaces of products such as shoe materials, clothes and the like, and is beneficial to meeting the demands of industrial production and users.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (4)
1. An anti-fouling TPU high-low temperature film is characterized in that: the anti-fouling PET film comprises a PET film layer, a release layer, an anti-fouling film layer, a pattern layer, a second adhesive layer, a TPU substrate layer, a first adhesive layer and a release film layer from top to bottom; the anti-fouling film layer is a transparent amphiphobic film layer, the transparent amphiphobic film layer is formed by coating transparent amphiphobic paint, and the transparent amphiphobic paint comprises the following raw materials in parts by weight: 7-10 parts of silicon dioxide nano particles, 8-15 parts of silane coupling agent, 4-14 parts of epoxy resin, 7-12 parts of polyurethane resin, 15-40 parts of dispersing agent, 20-45 parts of stabilizer, 0.5-1.0 part of regulator, 2-10 parts of curing agent and 10-30 parts of deionized water;
the preparation method of the transparent amphiphobic coating comprises the following steps:
(1) Adding the silicon dioxide nano particles into a dispersing agent, uniformly mixing, and carrying out ultrasonic treatment for 10-40min to obtain a solution A;
(2) Mixing deionized water and a stabilizer, stirring uniformly, adding a regulator, regulating the pH value to be 2-5 to obtain a solution B, adding a silane coupling agent into the solution B, and pre-hydrolyzing for 30-60min to obtain a silane coupling agent hydrolysate;
(3) Mixing the solution A with the silane coupling agent hydrolysate, and stirring for 2-5 hours at 45-75 ℃ in a magnetic stirrer to obtain a solution C;
(4) Adding polyurethane resin into the solution C, performing ultrasonic treatment for 10-30min, and stirring for 5-20min by using a magnetic stirrer to obtain a solution D;
(5) Adding epoxy resin and a curing agent into the solution D, mixing, and carrying out ultrasonic treatment for 20-60min to obtain a transparent amphiphobic coating;
the silica nanoparticles are hydrophobic silica nanoparticles; the silane coupling agent is a fluorine-containing silane coupling agent.
2. An anti-fouling TPU high and low temperature film according to claim 1, wherein: the epoxy resin is bisphenol A type epoxy resin.
3. An anti-fouling TPU high and low temperature film according to claim 1, wherein: the dispersing agent is at least one of toluene, xylene, acetic acid or ethyl acetate.
4. A process for preparing an anti-fouling TPU high and low temperature film according to any one of claims 1-3 comprising the steps of:
(S1) taking a TPU substrate layer, coating hot melt adhesive on the lower surface of the TPU substrate layer, drying to form a first adhesive layer, and attaching a release film on the lower surface of the first adhesive layer to form a release film layer;
(S2) taking a PET film layer, coating a release layer coating on the upper surface of the PET film layer, drying to form a release layer, coating a transparent amphiphobic coating on the upper surface of the release layer, drying to form an anti-fouling film layer, and printing on the upper surface of the anti-fouling film layer to form a pattern layer;
And (S3) coating a hot melt adhesive on the upper surface of the TPU substrate layer, drying to form a second adhesive layer, attaching the pattern layer on the upper surface of the second adhesive layer, and drying to obtain the anti-fouling TPU high-low temperature film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310766959.5A CN116769413B (en) | 2023-06-27 | 2023-06-27 | Anti-fouling TPU high-low temperature film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310766959.5A CN116769413B (en) | 2023-06-27 | 2023-06-27 | Anti-fouling TPU high-low temperature film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116769413A CN116769413A (en) | 2023-09-19 |
| CN116769413B true CN116769413B (en) | 2024-04-19 |
Family
ID=87987606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310766959.5A Active CN116769413B (en) | 2023-06-27 | 2023-06-27 | Anti-fouling TPU high-low temperature film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116769413B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118003742B (en) * | 2024-04-08 | 2024-06-14 | 泉州市星达鞋服材料有限公司 | High-elasticity honeycomb TPU high-low temperature film and forming process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189706A (en) * | 2016-08-09 | 2016-12-07 | 河南大学 | A kind of super-hydrophobic resin-coated preparation method |
| CN108373609A (en) * | 2016-11-18 | 2018-08-07 | 北京易净星科技有限公司 | It is used to prepare the coating and its preparation and application of transparent hydrophobic coating |
| CN109306225A (en) * | 2018-08-23 | 2019-02-05 | 国网湖南省电力有限公司 | A kind of high-adhesion superhydrophobic coating and preparation method and application thereof |
| CN110204996A (en) * | 2019-06-18 | 2019-09-06 | 上海泰梧科技有限公司 | A kind of oil pipeline high abrasion corrosion-inhibiting coating and preparation method thereof |
| CN115785834A (en) * | 2022-11-28 | 2023-03-14 | 广东中鼎科技发展有限公司 | TPU high-low temperature film with repairing function and preparation method thereof |
-
2023
- 2023-06-27 CN CN202310766959.5A patent/CN116769413B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189706A (en) * | 2016-08-09 | 2016-12-07 | 河南大学 | A kind of super-hydrophobic resin-coated preparation method |
| CN108373609A (en) * | 2016-11-18 | 2018-08-07 | 北京易净星科技有限公司 | It is used to prepare the coating and its preparation and application of transparent hydrophobic coating |
| CN109306225A (en) * | 2018-08-23 | 2019-02-05 | 国网湖南省电力有限公司 | A kind of high-adhesion superhydrophobic coating and preparation method and application thereof |
| CN110204996A (en) * | 2019-06-18 | 2019-09-06 | 上海泰梧科技有限公司 | A kind of oil pipeline high abrasion corrosion-inhibiting coating and preparation method thereof |
| CN115785834A (en) * | 2022-11-28 | 2023-03-14 | 广东中鼎科技发展有限公司 | TPU high-low temperature film with repairing function and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116769413A (en) | 2023-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11149152B2 (en) | Durable hydrophilic-super-hydrophobic bipolar self-cleaning composite film, and preparation method therefor | |
| CN105348946B (en) | A kind of matte release film | |
| JP5078620B2 (en) | Hollow silica fine particles, composition for forming transparent film containing the same, and substrate with transparent film | |
| CN116769413B (en) | Anti-fouling TPU high-low temperature film and preparation method thereof | |
| CN112175520A (en) | Preparation method and application of a superhydrophobic, transparent and durable coating | |
| CN110180762A (en) | Appearance member with super-hydrophobic oleophobic coating and preparation method thereof and terminal | |
| CN106009021B (en) | A kind of preparation method of anti-reflection and anti-fingerprint coating film suitable for plastic substrate | |
| CN110484180B (en) | High-flexibility high-hardness low-warpage hardening glue, hardening protective film and preparation method | |
| CN103408990A (en) | A kind of nanoparticle superhydrophobic self-cleaning wall paint and preparation method thereof | |
| CN102286240A (en) | PE (Polyurethane) gloss white paint | |
| CN112708370B (en) | Anti-glare protective film and preparation method and application thereof | |
| Jeong et al. | Highly transparent, organic-inorganic hybrid UV-curable coating materials with amphiphobic characteristics | |
| CN113292906A (en) | Preparation and application of high-hardness wear-resistant coating | |
| CN115558391A (en) | A kind of waterproof wear-resisting coating and its preparation method, application | |
| CN105647251B (en) | A kind of waterproofing agent preparation method and applications for fibrous plate | |
| CN109054669A (en) | Mute black Wear-resistant, high-temperature resistant adhesive tape of one kind and preparation method thereof | |
| CN113736122A (en) | An ultra-smooth film with antistatic effect | |
| CN109130349A (en) | A kind of high definition is without scratch resistant PC material protective film of rainbow and preparation method thereof | |
| CN105368129A (en) | High-abrasion-resistance waterborne UV (ultraviolet)-curable carpentry coating and preparation method | |
| CN114854234B (en) | High-permeability high-wear-resistance hardening coating and preparation method thereof | |
| CN110408066A (en) | Environment protection damp-proof high abrasion finishing material and its preparation method and application | |
| CN105860826A (en) | Surface conditioning agent and adhesive membrane | |
| CN109943119A (en) | A kind of preparation method of the wear-resisting finishing varnish of stain resistant | |
| CN104945976A (en) | High-strength UV (Ultraviolet) curing coating for terrace | |
| CN104945980A (en) | Photocurable coating with improved thermal conductivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |