CN116622207B - Protective film for screen and preparation method thereof - Google Patents
Protective film for screen and preparation method thereof Download PDFInfo
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- CN116622207B CN116622207B CN202310608305.XA CN202310608305A CN116622207B CN 116622207 B CN116622207 B CN 116622207B CN 202310608305 A CN202310608305 A CN 202310608305A CN 116622207 B CN116622207 B CN 116622207B
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- polycarbonate
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- protective film
- screen
- polyhydroxy compound
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- 230000001681 protective effect Effects 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000004417 polycarbonate Substances 0.000 claims abstract description 75
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 74
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims abstract description 18
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 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 claims abstract description 11
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000007493 shaping process Methods 0.000 claims abstract description 7
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 7
- 229930003268 Vitamin C Natural products 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 235000019154 vitamin C Nutrition 0.000 claims description 7
- 239000011718 vitamin C Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 5
- 229930195725 Mannitol Natural products 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 235000010355 mannitol Nutrition 0.000 claims description 5
- 239000000594 mannitol Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 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 description 48
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 24
- 239000000463 material Substances 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- -1 mobile phones Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000703 anti-shock Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
The application relates to the technical field of surface protection films, and particularly discloses a screen protection film and a preparation method thereof. The screen protective film comprises the following raw materials in parts by weight: 25-35 parts of polycarbonate, 5-8 parts of tert-butylaminoethyl methacrylate, 6-10 parts of perfluorodecyltrimethoxysilane, 5-7 parts of inorganic nanoparticles, 5-8 parts of ultra-high molecular weight polyethylene, 8-12 parts of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester, 3-5 parts of calcium zinc stabilizer and 12-18 parts of polyhydroxy compound; the preparation method comprises the following steps: after the pretreatment of the polycarbonate and the inorganic nano particles, the raw materials are added and mixed uniformly at one time, and after heating, melting and extrusion, the screen protective film is obtained through shaping and cooling. The protective film for the screen can be used for the surface of an optical product and has the advantage of good friction resistance.
Description
Technical Field
The application relates to the technical field of surface protection films, in particular to a screen protection film and a preparation method thereof.
Background
With the development of technology, touch screen products such as mobile phones, tablet computers and optical touch screens have become indispensable articles for people to live, and in order to prevent the touch screen from being scratched or scratched by nails or other hard objects, most consumers attach a layer of high-quality and low-cost protective film to the touch screen.
The materials of the screen protection film are continuously updated, and the materials are developed into toughened glass films, TPU films, full-plastic composite films and the like which are mainstream in the past from initial PC (polycarbonate) films, PVC (polyvinyl chloride) films and PET (polyethylene terephthalate) films. In order to improve the sensory experience and vision protection of users, the screen protective film is not simple anti-falling and anti-shock any more, and more optical protective films with high transmittance, anti-dazzle, anti-blue light and the like are claimed. However, the screen protective film still has the problems of wear resistance, easy scratch occurrence, increased strength of eyes, eye fatigue and visual influence.
Disclosure of Invention
In order to improve the wear resistance of a screen protective film, the application provides a protective film for a screen and a preparation method thereof.
In a first aspect, the present application provides a protective film for a screen, which adopts the following technical scheme:
the screen protective film comprises the following raw materials in parts by weight: 25-40 parts of polycarbonate, 5-8 parts of tert-butylaminoethyl methacrylate, 6-10 parts of perfluorodecyltrimethoxysilane, 5-7 parts of inorganic nanoparticles, 5-8 parts of ultra-high molecular weight polyethylene, 8-12 parts of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester, 3-5 parts of calcium zinc stabilizer and 12-18 parts of polyhydroxy compound.
By adopting the technical scheme, polycarbonate and ultra-high molecular weight polyethylene are used as base materials of the protective film material, the ultra-high molecular weight polyethylene is selected to have the molecular weight of 170-300 ten thousand, the ultra-high molecular weight polyethylene with the molecular weight of more than 170 ten thousand has better wear resistance, the polyethylene with the higher molecular weight has better performance, but the processability is poor, the ultra-high molecular weight polyethylene has lower self friction coefficient when the molecular weight is between 170 ten thousand-300 ten thousand, the long linear structure of the ultra-high molecular weight polyethylene is blended and modified with the polycarbonate, the ultra-high molecular weight polyethylene is mutually wound and connected with hydroxyl compounds, the problem of poor wear resistance of the polycarbonate is solved, the friction resistance and the impact resistance of the product protective film are improved, and the added perfluoro decyl trimethoxysilane and the silicon-oxygen bond in the silane coupling agent can form Si-OH to participate in condensation reaction with the polyhydroxy compound to form an organic-inorganic double-layer structure, so that the wear resistance of the protective film is further enhanced.
Optionally, the polycarbonate is modified polycarbonate, and is obtained through modification treatment of aminopropyl triethoxysilane and tetramethyl ammonium acetate.
By adopting the technical scheme, the polycarbonate is aromatic polycarbonate, has excellent mechanical properties, good impact resistance and good processing property, but has smaller surface energy and poor adhesion with other raw materials, and the surface of the polycarbonate is modified to improve the reactivity and adhesion with other raw materials, and the reactivity of the surface of the polycarbonate is greatly improved by modifying the surface of the polycarbonate by aminopropyl triethoxy silane.
Optionally, the preparation method of the modified polycarbonate comprises the following steps:
(1) After adding isopropanol into the polycarbonate, cleaning the surface of the polycarbonate by ultrasonic waves;
(2) And (3) placing the cleaned polycarbonate into a hydrochloric acid solution, heating the polycarbonate to 100 ℃ in a water bath, stirring for 5-10min, fully washing and drying, immersing the polycarbonate into a mixed solution of aminopropyl triethoxysilane and tetramethylammonium acetate, and stirring for reaction to obtain the modified polycarbonate.
By adopting the technical scheme, isopropanol is added, simultaneously, the polycarbonate is subjected to ultrasonic treatment to remove dust and grease on the surface of the polycarbonate, hydrochloric acid hydrolyzes the polycarbonate to enable the surface of the polycarbonate to be carboxylated, better adhesiveness and reactivity are given to the surface of the polycarbonate, aminopropyl triethoxysilane and tetramethyl ammonium acetate undergo polycondensation reaction, active molecules occupy the surface of the polycarbonate, and the active molecules are closely arranged together through Van der Waals force and intermolecular hydrogen bonds to form an interface lubricating film, so that the surface friction coefficient of the protective film is reduced, and the friction resistance of the protective film is improved.
Optionally, the polyhydroxy compound is one of vitamin C and mannitol.
By adopting the technical scheme, the hydroxyl functional groups in the polyhydroxy compound provide long-term adhesion to the matrix, and can perform polycondensation reaction with the functional groups on the surface of the polycarbonate to form firm chemical bonds, so that the friction resistance of the protective film is improved.
Optionally, the inorganic nanoparticle is one of nano porcelain clay, nano alumina and nano silicon dioxide.
By adopting the technical scheme, the addition of a proper amount of inorganic nano particles obviously improves the hardness of the material, so that friction matters are difficult to press into the protective film, and the friction coefficient is reduced, thereby greatly improving the wear resistance and durability of the protective film.
Optionally, the particle size of the inorganic nanoparticle is 50-80nm.
By adopting the technical scheme, the size effect and macroscopic quantum tunneling effect of the nano inorganic ions can enable particles to penetrate into the vicinity of unsaturated bonds of a polymer chain, act with electron clouds of the unsaturated bonds, densify a network structure, and therefore the wear resistance and durability of the material are improved.
Optionally, the screen protective film raw material further comprises 3-5 parts of organic glass.
By adopting the technical scheme, the organic glass has good compatibility with polycarbonate, and the organic glass is used as a better thermoplastic plastic, has a soft long molecular chain and can greatly improve the toughness and the shock resistance of the protective film.
In a second aspect, the present application provides a method for preparing a protective film for a screen, which adopts the following technical scheme:
the preparation method of the protective film for the screen comprises the following preparation modes:
(1) Adding tert-butylaminoethyl methacrylate, perfluorodecyltrimethoxysilane and perfluorodecyltrimethoxysilane into polycarbonate, adding hydrochloric acid, heating in water bath to 80-100 ℃, and stirring for reaction to obtain pretreated polycarbonate;
(2) Immersing inorganic nano particles into 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester in advance, stirring for reaction, and filtering out for later use;
(3) Drying the pretreated polycarbonate obtained in the step (1) in an oven at 80-100 ℃, and controlling the moisture content of the polycarbonate to be less than 0.02%;
(4) And (3) adding the polycarbonate dried in the step (3), the ultra-high molecular weight polyethylene, the polyhydroxy compound and the calcium-zinc stabilizer into the mixture at one time, uniformly mixing the mixture, continuously extruding the mixture, and carrying out shaping and cooling to obtain the screen protective film.
Through adopting above-mentioned technical scheme, the moisture content in the dry control polycarbonate before extrusion, the existence of moisture leads to the fact the influence to follow-up reaction easily under high temperature, leads to the polycarbonate to take place the degradation, and the viscosity drops, leads to unable shaping, dries in advance in order to avoid the influence of moisture to the reaction. The material is subjected to solid state, molten state and solid state morphological change to obtain a final product, and each raw material component is subjected to chemical reaction in the molten state, so that the friction resistance and the impact resistance of the protective film are improved.
In summary, the application has the following beneficial effects:
1. the application adopts hydroxyl-containing polymer and polycarbonate surface to perform polycondensation reaction to form firm chemical bond, so that active molecules occupy each bonding position on the surface of the base material, and adsorbed molecules are tightly arranged together through intermolecular hydrogen bond and Van der Waals force, thereby forming a layer of uniformly distributed, tightly arranged and two-dimensional ordered structure on the surface of the base material, endowing the surface of the protective film with oil and water repellency, and improving the impact strength and wear resistance of the protective film.
2. In the application, tetramethyl ammonium acetate and aminopropyl triethoxy silane are preferably adopted to modify polycarbonate, and the tetramethyl ammonium acetate and the aminopropyl triethoxy silane have anionic functional groups and cationic functional groups, and can react with the polycarbonate to form a polycarbonate ion modified copolymer, so that the wear resistance and the fracture resistance of the protective film are improved, and the modified polycarbonate is combined with an organosilicon network and other raw materials to form a network structure of siloxane bonds with high crosslinking density, so that the protective film with good wear resistance is prepared.
Detailed Description
The present application will be described in further detail with reference to examples.
Ultra-high molecular weight polyethylene was purchased from the company of Corp. High pressure polyethylene was purchased from the Dongguan city Chang Pingrui abundant raw materials commercial sector; poly bisphenol A carbonate was purchased from North Chengfengcheng chemical Co.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Examples of preparation of starting materials and/or intermediates
Preparation example 1
A modified polycarbonate is prepared by the following steps:
(1) Adding 55kg of isopropanol into 40kg of poly bisphenol A carbonate, and carrying out ultrasonic treatment at 30KHZ for 20min to pretreat the surface of the poly bisphenol A carbonate;
(2) And (3) putting the pretreated poly bisphenol A carbonate into 50kg of hydrochloric acid solution, stirring for 5min, fully washing with water, drying, immersing into a mixed solution of 25kg of aminopropyl triethoxysilane and 25kg of tetramethyl ammonium acetate, and stirring for reaction to obtain the modified polycarbonate.
Preparation example 2
A modified polycarbonate is prepared by the following steps:
(1) Adding 55kg of isopropanol into 40kg of poly bisphenol A carbonate, and carrying out ultrasonic treatment at 30KHZ for 20min to pretreat the surface of the poly bisphenol A carbonate;
(2) And (3) putting the pretreated poly bisphenol A carbonate into 50kg of hydrochloric acid solution, stirring for 8min, fully washing and drying, immersing into a mixed solution of 26.5kg of aminopropyl triethoxysilane and 20kg of tetramethyl ammonium acetate, and stirring for reaction to obtain the modified polycarbonate.
Preparation example 3
A modified polycarbonate is prepared by the following steps:
(1) Adding 55kg of isopropanol into 40kg of poly bisphenol A carbonate, and carrying out ultrasonic treatment at 30KHZ for 20min to pretreat the surface of the poly bisphenol A carbonate;
(2) And (3) putting the pretreated poly bisphenol A carbonate into 50kg of hydrochloric acid solution, stirring for 8min, fully washing and drying, immersing into a mixed solution of 28kg of aminopropyl triethoxysilane and 22.5kg of tetramethyl ammonium acetate, and stirring for reaction to obtain the modified polycarbonate.
Examples
Example 1
A protective film for a screen, comprising the steps of:
(1) Adding 8kg of tert-butylaminoethyl methacrylate and 7kg of perfluorodecyl trimethoxy silane into 25kg of poly bisphenol A carbonate, adding hydrochloric acid, heating in a water bath to 80-100 ℃, and stirring for reaction for 10min to obtain pretreated polycarbonate;
(2) Immersing 5kg of nano porcelain clay into 12kg of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester in advance, stirring for reaction, and filtering out for later use;
(3) Drying the pretreated poly bisphenol A carbonate obtained in the step (1) in an oven at 80 ℃ to control the moisture content of the poly bisphenol A carbonate to be less than 0.02%;
(4) Uniformly mixing the dried poly bisphenol A carbonate in the step (3) with 8kg of ultra-high molecular weight polyethylene, 18kg of vitamin C and 5kg of calcium stearate, adding the mixture into a double-screw extruder at one time, continuously extruding at 230 ℃, shaping and cooling to obtain the screen protective film.
Example 2
A protective film for a screen, comprising the steps of:
(1) Adding 6.5kg of tert-butylaminoethyl methacrylate and 5kg of perfluorodecyl trimethoxy silane into 30kg of poly bisphenol A carbonate, adding hydrochloric acid, heating in a water bath to 100 ℃, and stirring for reaction for 10min to obtain pretreated polycarbonate;
(2) Immersing 6kg of nano porcelain clay into 10kg of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester in advance, stirring for reaction, and filtering out for later use;
(3) Drying the pretreated poly bisphenol A carbonate obtained in the step (1) in an oven at 80 ℃ to control the moisture content of the poly bisphenol A carbonate to be less than 0.02%;
(4) Uniformly mixing the dried poly bisphenol A carbonate in the step (3) with 6.5kg of ultra-high molecular weight polyethylene, 14kg of vitamin C and 3kg of calcium stearate, adding the mixture into a double-screw extruder at one time, continuously extruding at 230 ℃, shaping and cooling to obtain the screen protective film.
Example 3
(1) Adding 5kg of tert-butylaminoethyl methacrylate and 6kg of perfluorodecyl trimethoxy silane into 35kg of poly bisphenol A carbonate, adding hydrochloric acid, heating in a water bath to 90 ℃, and stirring for reaction for 10min to obtain pretreated poly bisphenol A carbonate;
(2) Immersing 7kg of nano porcelain clay into 8kg of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester in advance, stirring for reaction, and filtering out for later use;
(3) Drying the pretreated poly bisphenol A carbonate obtained in the step (1) in a drying oven at 100 ℃, and controlling the moisture content of the poly bisphenol A carbonate to be less than 0.02%;
(4) Uniformly mixing the dried poly bisphenol A carbonate in the step (3) with 5kg of ultra-high molecular weight polyethylene, 12kg of vitamin C and 4kg of zinc stearate, adding the mixture into a double-screw extruder at one time, continuously extruding at 230 ℃, shaping and cooling to obtain the screen protective film.
Example 4
The protective film for a screen is different from example 1 in that the polycarbonate used in this example is a modified polycarbonate prepared in preparation example 1.
Example 5
The protective film for a screen is different from example 1 in that the polycarbonate used in this example is a modified polycarbonate prepared in preparation example 2.
Example 6
The protective film for a screen is different from example 1 in that the polycarbonate used in this example is a modified polycarbonate prepared in preparation example 3.
Example 7
A protective film for a screen is different from example 6 in that the polyhydroxy compound used in this example is mannitol.
Example 8
A protective film for a screen is different from example 7 in that the nanoparticles used in this example are nano alumina.
Example 9
A protective film for a screen is different from example 7 in that the nanoparticles used in this example are nanosilica.
Example 10
A protective film for a screen was different from example 8 in that 3kg of organic glass was further added in this example.
Example 11
A protective film for a screen was different from example 8 in that 5kg of organic glass was also added in this example.
Comparative example
Comparative example 1
A protective film for a screen is different from example 1 in that the raw material is replaced with an equivalent amount of polyethylene carbonate to the poly bisphenol A carbonate.
Comparative example 2
A protective film for a screen is different from example 1 in that a polyhydroxy compound is substituted with an equivalent amount of polycarbonate in the raw material.
Comparative example 3
A protective film for a screen is different from example 1 in that the ultra-high molecular weight polyethylene is replaced with the same amount of high pressure polyethylene in the raw material.
Performance test
Detection method/test method abrasion resistance test: detecting the abrasion resistance of the screen protective film according to the abrasion resistance test method in Q/Ali 00006-2017 technical Specification of Mobile phone protective film, and reacting the abrasion resistance of the protective film with the change of the contact angle of water before and after abrasion;
impact resistance: the impact resistance test of the protective film is carried out by using a ball falling impact tester MY-LQT-1800, and the ball falling control method comprises the following steps: direct current electromagnetic control; ball height: 60cm; the impact test was performed using 100g, 150g, 300g and 500g of test balls, respectively, and the damage condition of the protective film was observed, and the maximum impact energy that the protective film can withstand was calculated.
TABLE 1 Performance test experiments
As can be seen from a combination of example 1 and comparative examples 1-2 and Table 1, the experimental data of example 1 are better than those of comparative examples 1-2, indicating that perfluorodecyl trimethoxysilane reacts with high molecular weight polyethylene of the base material and polycarbonate to provide a strong hydrophobic and oleophobic ability to the surface, and reactive groups are provided for the reaction between the raw materials to further react the polycarbonate with hydroxyl compounds to enhance the abrasion resistance of the surface of the protective film.
As can be seen from the combination of example 1 and comparative example 3 and the table 1, each test data of example 1 is superior to comparative example 3, indicating that the abrasion resistance of the protective film is reduced and the strength is also reduced in the absence of blending reinforcement of ultra-high molecular weight polyethylene.
As can be seen from the combination of examples 1 to 6 and table 1, the data of examples 4 to 6 are better than those of examples 1 to 3, which shows that the modified polycarbonate-made protective film has better reactivity and good compatibility with other components, so that the prepared protective film has better surface friction resistance and impact resistance.
It can be seen from the combination of examples 6 to 7 and Table 1 that the protective film for screen having good abrasion resistance can be obtained when vitamin C and mannitol are used as the polyhydroxy compound; as can be seen from the combination of examples 7 to 9 and Table 1, a protective film for a screen having a good friction resistance can be obtained by using any one of inorganic particles of nano porcelain clay, nano alumina and nano silica.
As can be seen from the combination of examples 8 and examples 10 to 11 and table 1, each test data of examples 9 to 10 is superior to example 8, which shows that when the organic glass is added, the system can form a good chemical reaction with the organic glass to fuse the superior performance of the organic glass, and further improve the wear resistance and impact resistance of the protective film.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (5)
1. The screen protective film is characterized by comprising the following raw materials in parts by weight: 25-35 parts of polycarbonate, 5-7 parts of inorganic nano particles, 5-8 parts of ultra-high molecular weight polyethylene, 8-12 parts of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester, 3-5 parts of calcium zinc stabilizer and 12-18 parts of polyhydroxy compound; the polycarbonate is obtained through pretreatment of tert-butylaminoethyl methacrylate and perfluorodecyltrimethoxysilane, and the pretreatment steps are as follows: adding tert-butylaminoethyl methacrylate and perfluorodecyltrimethoxysilane into polycarbonate, adding hydrochloric acid, heating in water bath to 80-100 ℃, and stirring for reaction to obtain pretreated polycarbonate; the polyhydroxy compound is one of vitamin C and mannitol; the inorganic nano particles are one of nano porcelain clay, nano alumina and nano silicon dioxide.
2. The screen protective film is characterized by comprising the following raw materials in parts by weight: 25-35 parts of polycarbonate, 5-7 parts of inorganic nano particles, 5-8 parts of ultra-high molecular weight polyethylene, 8-12 parts of 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester, 3-5 parts of calcium zinc stabilizer and 12-18 parts of polyhydroxy compound, wherein the polycarbonate is modified polycarbonate, and is obtained through aminopropyl triethoxysilane and tetramethyl ammonium acetate modification treatment, and the modification treatment comprises the following steps: (1) After adding isopropanol into the polycarbonate, cleaning the surface of the polycarbonate by ultrasonic waves; (2) Placing the cleaned polycarbonate into a hydrochloric acid solution, heating the polycarbonate to 100 ℃ in a water bath, stirring for 5-10min, fully washing and drying, immersing the polycarbonate into a mixed solution of aminopropyl triethoxysilane and tetramethyl ammonium acetate, and stirring for reaction to obtain modified polycarbonate; the polyhydroxy compound is one of vitamin C and mannitol; the inorganic nano particles are one of nano porcelain clay, nano alumina and nano silicon dioxide.
3. A protective film for a screen according to any one of claims 1 to 2, characterized in that: the particle size of the inorganic nano particles is 50-80nm.
4. A protective film for a screen according to claim 2, wherein: the screen protective film raw material also comprises 3-5 parts of organic glass.
5. A method for producing a protective film for a screen according to any one of claims 1 to 2, comprising the following production modes:
(1) Taking pretreated or modified polycarbonate for later use;
(2) Immersing inorganic nano particles into 3- (trimethoxysilyl) propyl-2-methyl-2-acrylic ester in advance, stirring for reaction, and filtering out for later use;
(3) Drying the polycarbonate in the step (1) in an oven at 80-100 ℃ and controlling the moisture content of the polycarbonate to be less than 0.02%;
(4) And (3) adding the polycarbonate dried in the step (3), the ultra-high molecular weight polyethylene, the polyhydroxy compound and the calcium-zinc stabilizer into the mixture at one time, uniformly mixing the mixture, continuously extruding the mixture, and carrying out shaping and cooling to obtain the screen protective film.
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