CN117141015A - Surface waterproof rubbing process of mobile phone shell based on glass fiber epoxy resin plate - Google Patents
Surface waterproof rubbing process of mobile phone shell based on glass fiber epoxy resin plate Download PDFInfo
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- CN117141015A CN117141015A CN202311114054.6A CN202311114054A CN117141015A CN 117141015 A CN117141015 A CN 117141015A CN 202311114054 A CN202311114054 A CN 202311114054A CN 117141015 A CN117141015 A CN 117141015A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 129
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 129
- 239000003365 glass fiber Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000003292 glue Substances 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000003973 paint Substances 0.000 claims abstract description 25
- 239000004744 fabric Substances 0.000 claims abstract description 24
- 238000012545 processing Methods 0.000 claims abstract description 18
- 238000007731 hot pressing Methods 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 102
- 229920005989 resin Polymers 0.000 claims description 62
- 239000011347 resin Substances 0.000 claims description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 53
- 229920005862 polyol Polymers 0.000 claims description 51
- 150000003077 polyols Chemical class 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 34
- 238000005507 spraying Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 30
- 229910021389 graphene Inorganic materials 0.000 claims description 30
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 28
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000004814 polyurethane Substances 0.000 claims description 24
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 20
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 17
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 238000004049 embossing Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000007046 ethoxylation reaction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 239000012779 reinforcing material Substances 0.000 abstract description 2
- 230000037452 priming Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 compound ethoxylated pentaerythritol Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000012360 testing method Methods 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
- C08J2363/00—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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The application relates to the technical field of mobile phone shells, in particular to a surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin plate. According to the scheme, glass fiber cloth is used as a reinforcing material, glue solution is coated on two sides of the glass fiber cloth, after solidification, multi-layer hot pressing is carried out, a mobile phone shell substrate is obtained, then priming paint and finishing paint are sprayed on the surface of the mobile phone shell substrate, a rubbing process is adopted to form textures, and a protective film is coated after gloss oil is sprayed, so that the mobile phone shell with waterproof surface is obtained. The application discloses a waterproof rubbing process for the surface of a mobile phone shell based on a glass fiber epoxy resin plate, which is reasonable in process design, proper in glue solution component adjustment, and the prepared mobile phone shell not only has excellent strength and waterproof performance, but also has excellent mechanical properties such as compressive strength, can be widely applied to processing of mobile phones or other electronic product shells, and has higher practicability.
Description
Technical Field
The application relates to the technical field of mobile phone shells, in particular to a surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin plate.
Background
With the development of social economy, consumers have increasingly higher requirements on the appearance, texture, strength and the like of the outer shell of the electronic equipment, so that the material design and process adjustment of the outer shell of the mobile phone become research and development projects focused by enterprises, glass fiber reinforced epoxy resin composite boards are generally adopted as the processing raw materials of the mobile phone shell in the existing market, but the conventional glass fiber reinforced epoxy resin composite boards have poor water resistance and cannot meet the actual processing requirements in strength.
Based on the situation, the application discloses a surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin plate, so as to provide a mobile phone shell with excellent water resistance and high strength, and discloses a surface specific processing process of the mobile phone shell, so as to solve the problems in the prior art.
Disclosure of Invention
The application aims to provide a waterproof rubbing process for the surface of a mobile phone shell based on a glass fiber epoxy resin plate, so as to solve the problems in the background art.
In order to solve the technical problems, the application provides the following technical scheme:
a waterproof rubbing process for the surface of a mobile phone shell based on a glass fiber epoxy resin plate comprises the following steps:
(1) Taking polyol, vacuum dehydrating for 20-30 min, mixing the polyol with a catalyst after dehydrating, uniformly stirring, heating to 60-65 ℃, slowly dropwise adding epichlorohydrin for 2-2.5 h, reacting for 6-8 h under heat preservation, removing unreacted epichlorohydrin, cooling to 40-45 ℃, diluting with toluene, adding solid sodium hydroxide, reacting for 5-6 h under heat preservation, filtering to collect a product, extracting an organic phase, washing and drying to obtain branched epoxy resin;
when the polyol is ethoxylated pentaerythritol with molecular weight of 600-800, the branched epoxy resin A is obtained by reaction; when the polyol is ethoxylation trimethylol propane with the molecular weight of 1000-1200, the branched epoxy resin B is obtained by reaction;
(2) Mixing epoxy resin, branched epoxy resin A and branched epoxy resin B to obtain compound resin, adding a curing agent and benzyl dimethylamine into the compound resin, and uniformly stirring to obtain a glue solution;
drying glass fiber cloth at 100-110 ℃ to remove water, coating glue solution on two sides of the glass fiber cloth, and curing at 110-120 ℃ to obtain a prepreg; stacking and paving a plurality of prepregs, and performing hot pressing and compounding to obtain a mobile phone shell substrate;
(3) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
In a more optimized scheme, in the step (1), the molar ratio of hydroxyl groups, epichlorohydrin and solid sodium hydroxide of the polyol is 1: (1.1-1.3): (1-1.1).
In the more optimized scheme, in the step (2), the preparation steps of the curing agent are as follows:
mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 1-2 hours in a nitrogen environment, wherein the reaction time is 70-75 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer;
and mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 5-10 ℃, adding polyurethane prepolymer, reacting for 2-2.5 h, and distilling to remove the solvent to obtain the curing agent.
The optimized scheme is that the compound alcohol is prepared by mixing ethoxylated pentaerythritol with the molecular weight of 300-400 and ethoxylated pentaerythritol with the molecular weight of 600-800, and the mass ratio is 1:1, a step of; the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1: (9-10).
In the more optimized scheme, in the step (2), the mass ratio of the epoxy resin E-51 to the branched epoxy resin A to the branched epoxy resin B is 3:2:1, a step of; the dosage of the benzyl dimethylamine is 0.3 to 0.4 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1.
in the step (2), the hot pressing temperature is 130-140 ℃ and the pressure is 5-10 MPa during hot pressing and compounding; the coating amount of the glue solution is 150-250 g/m 2 。
In the more optimized scheme, in the step (2), the glue solution contains fluorinated graphene and oxidized graphene, wherein the dosage of the fluorinated graphene is 0.5-0.8 wt% of the total amount of the compound resin, and the dosage of the oxidized graphene is 0.8-1 wt% of the total amount of the compound resin;
the surface of the fluorinated graphene and the surface of the oxidized graphene are treated by a silane coupling agent, and the specific steps are as follows: KH-560, methanol and deionized water are taken, and the volume ratio is 5:1:1, mixing, ultrasonic dispersing for 10-20 min, hydrolyzing for 20-24 h at 30-40 ℃, adding fluorinated graphene or oxidized graphene, reacting for 3-4 h at 80-85 ℃ in water bath, centrifugally washing, and freeze drying.
In a more optimized scheme, in the reaction, the catalyst is dibutyl tin dilaurate.
And in a more optimized scheme, the epoxy resin is epoxy resin E-44 or epoxy resin E-51.
Compared with the prior art, the application has the following beneficial effects:
the application discloses a waterproof rubbing process for the surface of a mobile phone shell based on a glass fiber epoxy resin plate, which adopts a scheme that glass fiber cloth is used as a reinforcing material, glue solution is coated on two sides of the glass fiber cloth, after solidification, multi-layer hot pressing is carried out, a mobile phone shell substrate is obtained, and then primer is sprayed on one side surface of the mobile phone shell substrate, and baking and solidification are carried out; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain a mobile phone shell with a waterproof surface; the application mainly creates the processing technology of the mobile phone shell substrate, the finishing paint, the primer, the protective film, the PU pearl lacquer and the UV glue which are involved in the subsequent technology are all available products, the components can be selected from acrylic esters, polyurethane, epoxy resins and the like, and the components can be specifically selected according to the requirements of customers and are not described herein.
In the scheme, the application improves the glue solution component, takes ethoxylated pentaerythritol with the molecular weight of 600-800 as a reaction component, and reacts with epichlorohydrin for epoxidation so as to generate the polyether epoxy resin (branched epoxy resin A) with a branched structure, wherein the branched epoxy resin A has a cross structure and is in a branched structure; meanwhile, the scheme takes ethoxylated trimethylolpropane with the molecular weight of 1000-1200 as a reaction component, and the ethoxylated trimethylolpropane reacts with epichlorohydrin for epoxidation to generate Y-shaped polyether epoxy resin (branched epoxy resin B) with a three-fork structure, and the Y-shaped polyether epoxy resin and the branched epoxy resin are mutually compounded, and a branched flexible molecular chain is introduced, so that the epoxy resin can be effectively toughened and reinforced by a system, and meanwhile, the crosslinking density of the system can be improved in the subsequent crosslinking process, so that the strength and the comprehensive mechanical property of a mobile phone shell substrate are improved, and the water resistance of a product is also improved.
On the basis, the scheme adjusts the preparation method of the curing agent, which is different from the conventional small molecular curing agent, the scheme is to compound ethoxylated pentaerythritol with the molecular weight of 300-400 and ethoxylated pentaerythritol with the molecular weight of 600-800, firstly, compound alcohol reacts with isocyanate groups, terminal isocyanate groups are introduced, and then the compound alcohol reacts with small molecular amine, so that the flexible curing agent is generated.
Meanwhile, the proposal adds the fluorinated graphene and the oxidized graphene into the glue solution, has a multi-layer laminated structure, can effectively realize the separation, and further improves the water resistance and corrosion resistance of the product.
The application discloses a waterproof rubbing process for the surface of a mobile phone shell based on a glass fiber epoxy resin plate, which is reasonable in process design, proper in glue solution component adjustment, and the prepared mobile phone shell not only has excellent strength and waterproof performance, but also has excellent mechanical properties such as compressive strength, can be widely applied to processing of mobile phones or other electronic product shells, and has higher practicability.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In this example, ethoxylated pentaerythritol having a molecular weight of 600 to 800: average molecular weight 797, average reaction of pentaerythritol with 15 ethylene oxide per molecule, PP150; ethoxylated trimethylolpropane with molecular weight 1000-1200: average molecular weight 1014, average reaction of 20 ethylene oxide per trimethylolpropane molecule, TP200; ethoxylated pentaerythritol with a molecular weight of 300-400: an average molecular weight of 355, average of 5 ethylene oxide reactions per pentaerythritol molecule, PP50; all three are provided by perstorpoab company, sweden. The epoxy resin is epoxy resin E-51. The glass fiber cloth is 2116 and has a thickness of 0.1mm. The product number of the fluorinated graphene is 100834, and the product number is XF096; the graphene oxide is 102185 and is provided by XF224-1, and is provided by Jiangsu Xianfeng nano materials.
Example 1:
the waterproof rubbing process for the surface of the mobile phone shell based on the glass fiber epoxy resin plate comprises the following steps:
(1) Taking polyol, vacuum dehydrating for 20min, mixing the polyol with a catalyst after dehydrating, uniformly stirring, heating to 60 ℃, slowly dropwise adding epichlorohydrin for 2h, carrying out heat preservation reaction for 8h, removing unreacted epichlorohydrin, cooling to 40 ℃, diluting with toluene, adding solid sodium hydroxide, carrying out heat preservation reaction for 5h, carrying out suction filtration, collecting a product, extracting an organic phase, washing and drying to obtain the branched epoxy resin. The catalyst was dibutyltin dilaurate in an amount of 0.05wt% of the polyol.
When the polyol is ethoxylated pentaerythritol with a molecular weight of 797, reacting to obtain branched epoxy resin A; when the polyol is ethoxylated trimethylol propane of molecular weight 1014, the reaction yields branched epoxy resin B; the molar ratio of hydroxyl groups, epichlorohydrin and solid sodium hydroxide of the polyol is 1:1.3:1.1.
(2) Mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 1h in a nitrogen environment, wherein the reaction time is 75 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer; and (3) mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 10 ℃, adding polyurethane prepolymer, reacting for 2 hours, and distilling to remove the solvent to obtain the curing agent.
Wherein the compound alcohol is prepared by mixing ethoxylated pentaerythritol with a molecular weight of 355 and ethoxylated pentaerythritol with a molecular weight of 797, and the mass ratio is 1:1, a step of; the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1:10. the catalyst is dibutyl tin dilaurate, and the dosage is 0.05wt% of the total mass of the compound alcohol and isophorone diisocyanate.
(3) Mixing epoxy resin, branched epoxy resin A and branched epoxy resin B to obtain compound resin, adding a curing agent and benzyl dimethylamine into the compound resin based on 100g of the compound resin, and uniformly stirring to obtain a glue solution; the mass ratio of the epoxy resin E-51 to the branched epoxy resin A to the branched epoxy resin B is 3:2:1, a step of; the dosage of the benzyl dimethylamine is 0.3 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1.
drying glass fiber cloth at 110 ℃ to remove water, coating glue solution on two sides of the glass fiber cloth, and curing at 120 ℃ to obtain a prepreg; the three prepregs are stacked, hot-pressed and compounded, wherein the hot-pressing temperature is 130 ℃ and the pressure is 5MPa; the coating amount of the glue solution is 250g/m 2 Obtaining a handA chassis base plate;
(4) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
Example 2:
the waterproof rubbing process for the surface of the mobile phone shell based on the glass fiber epoxy resin plate comprises the following steps:
(1) Taking polyol, vacuum dehydrating for 20min, mixing the polyol with a catalyst after dehydrating, uniformly stirring, heating to 65 ℃, slowly dropwise adding epichlorohydrin for 2h, carrying out heat preservation reaction for 7h, removing unreacted epichlorohydrin, cooling to 45 ℃, diluting with toluene, adding solid sodium hydroxide, carrying out heat preservation reaction for 5.5h, carrying out suction filtration, collecting a product, extracting an organic phase, washing and drying to obtain branched epoxy resin. The catalyst was dibutyltin dilaurate in an amount of 0.05wt% of the polyol.
When the polyol is ethoxylated pentaerythritol with a molecular weight of 797, reacting to obtain branched epoxy resin A; when the polyol is ethoxylated trimethylol propane of molecular weight 1014, the reaction yields branched epoxy resin B; the molar ratio of hydroxyl groups, epichlorohydrin and solid sodium hydroxide of the polyol is 1:1.2:1.1.
(2) Mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 1.5 hours in a nitrogen environment, wherein the reaction time is 75 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer; and mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 10 ℃, adding polyurethane prepolymer, reacting for 2.5 hours, and distilling to remove the solvent to obtain the curing agent.
Wherein the compound alcohol is prepared by mixing ethoxylated pentaerythritol with a molecular weight of 355 and ethoxylated pentaerythritol with a molecular weight of 797, and the mass ratio is 1:1, a step of; the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1:10. the catalyst is dibutyl tin dilaurate, and the dosage is 0.05wt% of the total mass of the compound alcohol and isophorone diisocyanate.
(3) Mixing epoxy resin, branched epoxy resin A and branched epoxy resin B to obtain compound resin, adding a curing agent and benzyl dimethylamine into the compound resin based on 100g of the compound resin, and uniformly stirring to obtain a glue solution; the mass ratio of the epoxy resin E-51 to the branched epoxy resin A to the branched epoxy resin B is 3:2:1, a step of; the dosage of the benzyl dimethylamine is 0.3 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1.
drying glass fiber cloth at 110 ℃ to remove water, coating glue solution on two sides of the glass fiber cloth, and curing at 120 ℃ to obtain a prepreg; the three prepregs are stacked, hot-pressed and compounded, wherein the hot-pressing temperature is 135 ℃ and the pressure is 5MPa; the coating amount of the glue solution is 250g/m 2 Obtaining a mobile phone shell substrate;
(4) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
Example 3:
the waterproof rubbing process for the surface of the mobile phone shell based on the glass fiber epoxy resin plate comprises the following steps:
(1) Taking polyol, vacuum dehydrating for 20min, mixing the polyol with a catalyst after dehydrating, uniformly stirring, heating to 65 ℃, slowly dropwise adding epichlorohydrin for 2h, carrying out heat preservation reaction for 6h, removing unreacted epichlorohydrin, cooling to 45 ℃, diluting with toluene, adding solid sodium hydroxide, carrying out heat preservation reaction for 6h, carrying out suction filtration, collecting a product, extracting an organic phase, washing and drying to obtain the branched epoxy resin. The catalyst was dibutyltin dilaurate in an amount of 0.05wt% of the polyol.
When the polyol is ethoxylated pentaerythritol with a molecular weight of 797, reacting to obtain branched epoxy resin A; when the polyol is ethoxylated trimethylol propane of molecular weight 1014, the reaction yields branched epoxy resin B; the molar ratio of hydroxyl groups, epichlorohydrin and solid sodium hydroxide of the polyol is 1:1.3:1.0.
(2) Mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 2 hours in a nitrogen environment at 70 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer; and mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 8 ℃, adding polyurethane prepolymer, reacting for 2.2 hours, and distilling to remove a solvent to obtain the curing agent.
Wherein the compound alcohol is prepared by mixing ethoxylated pentaerythritol with a molecular weight of 355 and ethoxylated pentaerythritol with a molecular weight of 797, and the mass ratio is 1:1, a step of; the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1:10. the catalyst is dibutyl tin dilaurate, and the dosage is 0.05wt% of the total mass of the compound alcohol and isophorone diisocyanate.
(3) Mixing epoxy resin, branched epoxy resin A and branched epoxy resin B to obtain compound resin, adding a curing agent and benzyl dimethylamine into the compound resin based on 100g of the compound resin, and uniformly stirring to obtain a glue solution; the mass ratio of the epoxy resin E-51 to the branched epoxy resin A to the branched epoxy resin B is 3:2:1, a step of; the dosage of the benzyl dimethylamine is 0.3 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1.
drying glass fiber cloth at 110 ℃ to remove water, coating glue solution on two sides of the glass fiber cloth, and curing at 120 ℃ to obtain a prepreg; the three prepregs are stacked, hot-pressed and compounded, wherein the hot-pressing temperature is 140 ℃ and the pressure is 5MPa; the coating amount of the glue solution is 250g/m 2 Obtaining a mobile phone shell substrate;
(4) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
Example 4:
the waterproof rubbing process for the surface of the mobile phone shell based on the glass fiber epoxy resin plate comprises the following steps:
(1) Taking polyol, vacuum dehydrating for 20min, mixing the polyol with a catalyst after dehydrating, uniformly stirring, heating to 65 ℃, slowly dropwise adding epichlorohydrin for 2h, carrying out heat preservation reaction for 7h, removing unreacted epichlorohydrin, cooling to 45 ℃, diluting with toluene, adding solid sodium hydroxide, carrying out heat preservation reaction for 5.5h, carrying out suction filtration, collecting a product, extracting an organic phase, washing and drying to obtain branched epoxy resin. The catalyst was dibutyltin dilaurate in an amount of 0.05wt% of the polyol.
When the polyol is ethoxylated pentaerythritol with a molecular weight of 797, reacting to obtain branched epoxy resin A; when the polyol is ethoxylated trimethylol propane of molecular weight 1014, the reaction yields branched epoxy resin B; the molar ratio of hydroxyl groups, epichlorohydrin and solid sodium hydroxide of the polyol is 1:1.2:1.1.
(2) Mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 1.5 hours in a nitrogen environment, wherein the reaction time is 75 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer; and mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 10 ℃, adding polyurethane prepolymer, reacting for 2.5 hours, and distilling to remove the solvent to obtain the curing agent.
Wherein the compound alcohol is prepared by mixing ethoxylated pentaerythritol with a molecular weight of 355 and ethoxylated pentaerythritol with a molecular weight of 797, and the mass ratio is 1:1, a step of; the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1:10. the catalyst is dibutyl tin dilaurate, and the dosage is 0.05wt% of the total mass of the compound alcohol and isophorone diisocyanate.
(3) Mixing epoxy resin, branched epoxy resin A and branched epoxy resin B to obtain compound resin, adding a curing agent and benzyl dimethylamine into the compound resin based on 100g of the compound resin, uniformly stirring, adding fluorinated graphene treated by a surface silane coupling agent and oxidized graphene treated by the surface silane coupling agent, and uniformly stirring to obtain a glue solution; the mass ratio of the epoxy resin E-51 to the branched epoxy resin A to the branched epoxy resin B is 3:2:1, a step of; the dosage of the benzyl dimethylamine is 0.3 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1. the dosage of the fluorinated graphene is 0.5 weight percent of the total amount of the compound resin, and the dosage of the oxidized graphene is 0.8 weight percent of the total amount of the compound resin.
The treatment steps of the surface silane coupling agent of the fluorinated graphene and the oxidized graphene are as follows: KH-560, methanol and deionized water are taken, and the volume ratio is 5:1:1, mixing, ultrasonic dispersing for 15min, hydrolyzing at 40 ℃ for 20h, adding fluorinated graphene or oxidized graphene, reacting for 3h in a water bath at 85 ℃, centrifugally washing, and freeze-drying. The mass ratio of the material to KH-560 is 1:5.
drying glass fiber cloth at 110 ℃ to remove water, coating glue solution on two sides of the glass fiber cloth, and curing at 120 ℃ to obtain a prepreg; the three prepregs are stacked, hot-pressed and compounded, wherein the hot-pressing temperature is 140 ℃ and the pressure is 5MPa; the coating amount of the glue solution is 250g/m 2 Obtaining a mobile phone shell substrate;
(4) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
Comparative example 1: comparative example 1 in which the graphene oxide and the graphene fluoride in comparative example 1 were not treated with a silane coupling agent, the remaining steps were unchanged, with example 4 as a control group.
The waterproof rubbing process for the surface of the mobile phone shell based on the glass fiber epoxy resin plate comprises the following steps:
(1) Taking polyol, vacuum dehydrating for 20min, mixing the polyol with a catalyst after dehydrating, uniformly stirring, heating to 65 ℃, slowly dropwise adding epichlorohydrin for 2h, carrying out heat preservation reaction for 7h, removing unreacted epichlorohydrin, cooling to 45 ℃, diluting with toluene, adding solid sodium hydroxide, carrying out heat preservation reaction for 5.5h, carrying out suction filtration, collecting a product, extracting an organic phase, washing and drying to obtain branched epoxy resin. The catalyst was dibutyltin dilaurate in an amount of 0.05wt% of the polyol.
When the polyol is ethoxylated pentaerythritol with a molecular weight of 797, reacting to obtain branched epoxy resin A; when the polyol is ethoxylated trimethylol propane of molecular weight 1014, the reaction yields branched epoxy resin B; the molar ratio of hydroxyl groups, epichlorohydrin and solid sodium hydroxide of the polyol is 1:1.2:1.1.
(2) Mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 1.5 hours in a nitrogen environment, wherein the reaction time is 75 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer; and mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 10 ℃, adding polyurethane prepolymer, reacting for 2.5 hours, and distilling to remove the solvent to obtain the curing agent.
Wherein the compound alcohol is prepared by mixing ethoxylated pentaerythritol with a molecular weight of 355 and ethoxylated pentaerythritol with a molecular weight of 797, and the mass ratio is 1:1, a step of; the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1:10. the catalyst is dibutyl tin dilaurate, and the dosage is 0.05wt% of the total mass of the compound alcohol and isophorone diisocyanate.
(3) Mixing epoxy resin, branched epoxy resin A and branched epoxy resin B to obtain compound resin, adding a curing agent and benzyl dimethylamine into the compound resin based on 100g of the compound resin, uniformly stirring, adding fluorinated graphene and graphene oxide, and uniformly stirring to obtain a glue solution; the mass ratio of the epoxy resin E-51 to the branched epoxy resin A to the branched epoxy resin B is 3:2:1, a step of; the dosage of the benzyl dimethylamine is 0.3 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1. the dosage of the fluorinated graphene is 0.5 weight percent of the total amount of the compound resin, and the dosage of the oxidized graphene is 0.8 weight percent of the total amount of the compound resin.
Drying glass fiber cloth at 110 ℃ to remove water, coating glue solution on two sides of the glass fiber cloth, and curing at 120 ℃ to obtain a prepreg; the three prepregs are stacked, hot-pressed and compounded, wherein the hot-pressing temperature is 140 ℃ and the pressure is 5MPa; the coating amount of the glue solution is 250g/m 2 Obtaining a mobile phone shell substrate;
(4) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
Comparative example 2: comparative example 2 with example 4 as the control, no branched epoxy resin B was added in comparative example 2, the rest of the procedure being unchanged.
The waterproof rubbing process for the surface of the mobile phone shell based on the glass fiber epoxy resin plate comprises the following steps:
(1) Taking polyol, vacuum dehydrating for 20min, mixing the polyol with a catalyst after dehydrating, uniformly stirring, heating to 65 ℃, slowly dropwise adding epichlorohydrin for 2h, carrying out heat preservation reaction for 7h, removing unreacted epichlorohydrin, cooling to 45 ℃, diluting with toluene, adding solid sodium hydroxide, carrying out heat preservation reaction for 5.5h, carrying out suction filtration, collecting a product, extracting an organic phase, washing and drying to obtain branched epoxy resin. The catalyst was dibutyltin dilaurate in an amount of 0.05wt% of the polyol.
When the polyol is ethoxylated pentaerythritol with a molecular weight of 797, reacting to obtain branched epoxy resin A; the molar ratio of hydroxyl groups, epichlorohydrin and solid sodium hydroxide of the polyol is 1:1.2:1.1.
(2) Mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 1.5 hours in a nitrogen environment, wherein the reaction time is 75 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer; and mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 10 ℃, adding polyurethane prepolymer, reacting for 2.5 hours, and distilling to remove the solvent to obtain the curing agent.
Wherein the compound alcohol is prepared by mixing ethoxylated pentaerythritol with a molecular weight of 355 and ethoxylated pentaerythritol with a molecular weight of 797, and the mass ratio is 1:1, a step of; the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1:10. the catalyst is dibutyl tin dilaurate, and the dosage is 0.05wt% of the total mass of the compound alcohol and isophorone diisocyanate.
(3) Mixing epoxy resin and branched epoxy resin A to obtain compound resin, adding a curing agent and benzyl dimethylamine into the compound resin based on 100g of the compound resin, uniformly stirring, adding fluorinated graphene treated by a surface silane coupling agent and oxidized graphene treated by the surface silane coupling agent, and uniformly stirring to obtain a glue solution; the mass ratio of the epoxy resin E-51 to the branched epoxy resin A is 3:2; the dosage of the benzyl dimethylamine is 0.3 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1. the dosage of the fluorinated graphene is 0.5 weight percent of the total amount of the compound resin, and the dosage of the oxidized graphene is 0.8 weight percent of the total amount of the compound resin.
The treatment steps of the surface silane coupling agent of the fluorinated graphene and the oxidized graphene are as follows: KH-560, methanol and deionized water are taken, and the volume ratio is 5:1:1, mixing, ultrasonic dispersing for 15min, hydrolyzing at 40 ℃ for 20h, adding fluorinated graphene or oxidized graphene, reacting for 3h in a water bath at 85 ℃, centrifugally washing, and freeze-drying. The mass ratio of the material to KH-560 is 1:5.
drying glass fiber cloth at 110 ℃ to remove water, coating glue solution on two sides of the glass fiber cloth, and curing at 120 ℃ to obtain a prepreg; the three prepregs are stacked, hot-pressed and compounded, wherein the hot-pressing temperature is 140 ℃ and the pressure is 5MPa; the coating amount of the glue solution is 250g/m 2 Obtaining a mobile phone shell substrate;
(4) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
Comparative example 3: comparative example 3 in which example 4 was used as a control, the branched epoxy resin B and the branched epoxy resin a were not added in comparative example 3, and the remaining steps were unchanged.
The waterproof rubbing process for the surface of the mobile phone shell based on the glass fiber epoxy resin plate comprises the following steps:
(1) Mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 1.5 hours in a nitrogen environment, wherein the reaction time is 75 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer; and mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 10 ℃, adding polyurethane prepolymer, reacting for 2.5 hours, and distilling to remove the solvent to obtain the curing agent.
Wherein the compound alcohol is prepared by mixing ethoxylated pentaerythritol with a molecular weight of 355 and ethoxylated pentaerythritol with a molecular weight of 797, and the mass ratio is 1:1, a step of; the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1:10. the catalyst is dibutyl tin dilaurate, and the dosage is 0.05wt% of the total mass of the compound alcohol and isophorone diisocyanate.
(2) Taking epoxy resin as a compound resin, adding a curing agent and benzyl dimethylamine into the compound resin based on 100g of the compound resin, uniformly stirring, adding fluorinated graphene treated by a surface silane coupling agent and oxidized graphene treated by the surface silane coupling agent, and uniformly stirring to obtain a glue solution; the dosage of the benzyl dimethylamine is 0.3 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1. the dosage of the fluorinated graphene is 0.5 weight percent of the total amount of the compound resin, and the dosage of the oxidized graphene is 0.8 weight percent of the total amount of the compound resin.
The treatment steps of the surface silane coupling agent of the fluorinated graphene and the oxidized graphene are as follows: KH-560, methanol and deionized water are taken, and the volume ratio is 5:1:1, mixing, ultrasonic dispersing for 15min, hydrolyzing at 40 ℃ for 20h, adding fluorinated graphene or oxidized graphene, reacting for 3h in a water bath at 85 ℃, centrifugally washing, and freeze-drying. The mass ratio of the material to KH-560 is 1:5.
drying glass fiber cloth at 110 ℃ to remove water, coating glue solution on two sides of the glass fiber cloth, and curing at 120 ℃ to obtain a prepreg; the three prepregs are stacked, hot-pressed and compounded, wherein the hot-pressing temperature is 140 ℃ and the pressure is 5MPa; the coating amount of the glue solution is 250g/m 2 Obtaining a mobile phone shell substrate;
(3) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
Comparative example 4: comparative example 4 the curing agent preparation step was adjusted in comparative example 4 with example 4 as a control group, and the remaining steps were unchanged.
The waterproof rubbing process for the surface of the mobile phone shell based on the glass fiber epoxy resin plate comprises the following steps:
(1) Taking polyol, vacuum dehydrating for 20min, mixing the polyol with a catalyst after dehydrating, uniformly stirring, heating to 65 ℃, slowly dropwise adding epichlorohydrin for 2h, carrying out heat preservation reaction for 7h, removing unreacted epichlorohydrin, cooling to 45 ℃, diluting with toluene, adding solid sodium hydroxide, carrying out heat preservation reaction for 5.5h, carrying out suction filtration, collecting a product, extracting an organic phase, washing and drying to obtain branched epoxy resin. The catalyst was dibutyltin dilaurate in an amount of 0.05wt% of the polyol.
When the polyol is ethoxylated pentaerythritol with a molecular weight of 797, reacting to obtain branched epoxy resin A; when the polyol is ethoxylated trimethylol propane of molecular weight 1014, the reaction yields branched epoxy resin B; the molar ratio of hydroxyl groups, epichlorohydrin and solid sodium hydroxide of the polyol is 1:1.2:1.1.
(2) Mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 1.5 hours in a nitrogen environment, wherein the reaction time is 75 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer; and mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 10 ℃, adding polyurethane prepolymer, reacting for 2.5 hours, and distilling to remove the solvent to obtain the curing agent.
Wherein the compound alcohol is ethoxylated pentaerythritol with molecular weight 797, and the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1:10. the catalyst is dibutyl tin dilaurate, and the dosage is 0.05wt% of the total mass of the compound alcohol and isophorone diisocyanate.
(3) Mixing epoxy resin, branched epoxy resin A and branched epoxy resin B to obtain compound resin, adding a curing agent and benzyl dimethylamine into the compound resin based on 100g of the compound resin, uniformly stirring, adding fluorinated graphene treated by a surface silane coupling agent and oxidized graphene treated by the surface silane coupling agent, and uniformly stirring to obtain a glue solution; the mass ratio of the epoxy resin E-51 to the branched epoxy resin A to the branched epoxy resin B is 3:2:1, a step of; the dosage of the benzyl dimethylamine is 0.3 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1. the dosage of the fluorinated graphene is 0.5 weight percent of the total amount of the compound resin, and the dosage of the oxidized graphene is 0.8 weight percent of the total amount of the compound resin.
The treatment steps of the surface silane coupling agent of the fluorinated graphene and the oxidized graphene are as follows: KH-560, methanol and deionized water are taken, and the volume ratio is 5:1:1, mixing, ultrasonic dispersing for 15min, hydrolyzing at 40 ℃ for 20h, adding fluorinated graphene or oxidized graphene, reacting for 3h in a water bath at 85 ℃, centrifugally washing, and freeze-drying. The mass ratio of the material to KH-560 is 1:5.
drying glass fiber cloth at 110 ℃ to remove water, coating glue solution on two sides of the glass fiber cloth, and curing at 120 ℃ to obtain a prepreg; the three prepregs are stacked, hot-pressed and compounded, and the hot-pressing temperature is 14The temperature is 0 ℃ and the pressure is 5MPa; the coating amount of the glue solution is 250g/m 2 Obtaining a mobile phone shell substrate;
(4) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
Detection experiment:
performance tests were performed on the mobile phone case substrates according to the methods disclosed in examples 1 to 3 and comparative examples 1 to 4, and specifically as follows:
1. and placing the mobile phone shell substrate in deionized water, soaking for 7 hours, taking out and wiping the mobile phone shell substrate, recording the weight before and after the test, and calculating the water absorption rate.
2. The tensile strength of the cell phone case substrate was measured according to GB/T1447-2005 and was 250mm by 25mm in size with a loading speed of 2mm/min.
Conclusion: the application discloses a waterproof rubbing process for the surface of a mobile phone shell based on a glass fiber epoxy resin plate, which is reasonable in process design, proper in glue solution component adjustment, and the prepared mobile phone shell not only has excellent strength and waterproof performance, but also has excellent mechanical properties such as compressive strength, can be widely applied to processing of mobile phones or other electronic product shells, and has higher practicability.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (9)
1. The waterproof rubbing process for the surface of the mobile phone shell based on the glass fiber epoxy resin plate is characterized by comprising the following steps of: the method comprises the following steps:
(1) Taking polyol, vacuum dehydrating for 20-30 min, mixing the polyol with a catalyst after dehydrating, uniformly stirring, heating to 60-65 ℃, slowly dropwise adding epichlorohydrin, reacting for 6-8 h under heat preservation, removing unreacted epichlorohydrin, cooling to 40-45 ℃, diluting with toluene, adding solid sodium hydroxide, reacting for 5-6 h under heat preservation, filtering, collecting a product, extracting an organic phase, washing and drying to obtain branched epoxy resin;
when the polyol is ethoxylated pentaerythritol with molecular weight of 600-800, the branched epoxy resin A is obtained by reaction; when the polyol is ethoxylation trimethylol propane with the molecular weight of 1000-1200, the branched epoxy resin B is obtained by reaction;
(2) Mixing epoxy resin, branched epoxy resin A and branched epoxy resin B to obtain compound resin, adding a curing agent and benzyl dimethylamine into the compound resin, and uniformly stirring to obtain a glue solution;
arranging glass fiber at 100-110 ℃ for drying, coating glue solution on two sides of the glass fiber cloth, and curing at 110-120 ℃ to obtain a prepreg; stacking and paving a plurality of prepregs, and performing hot pressing and compounding to obtain a mobile phone shell substrate;
(3) Taking a mobile phone shell substrate, spraying primer on one side surface, and baking and curing; coating UV glue on the texture surface of the inner texture mold, and attaching the mobile phone shell substrate sprayed with the primer to the UV glue surface, and performing ultraviolet curing to form an inner texture layer; spraying PU (polyurethane) pearl paint on the surface of the inner texture layer, baking and curing, spraying finishing paint, baking and curing, embossing to form an outer texture layer, covering a protective film, and CNC (computer numerical control) processing and forming to obtain the finished mobile phone shell.
2. The surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin board material, which is characterized in that: in the step (1), the molar ratio of hydroxyl groups, epichlorohydrin and solid sodium hydroxide of the polyol is 1: (1.1-1.3): (1-1.1).
3. The surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin board material, which is characterized in that: in the step (2), the preparation steps of the curing agent are as follows:
mixing isophorone diisocyanate, compound alcohol and a catalyst, reacting for 1-2 hours in a nitrogen environment, wherein the reaction time is 70-75 ℃, and adding ethyl acetate to obtain a polyurethane prepolymer;
and mixing trimethyl hexamethylenediamine and ethyl acetate in a nitrogen environment, uniformly stirring, cooling to 5-10 ℃, adding polyurethane prepolymer, reacting for 2-2.5 h, and distilling to remove the solvent to obtain the curing agent.
4. The surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin plate, which is characterized in that: the compound alcohol is prepared by mixing ethoxylated pentaerythritol with the molecular weight of 300-400 and ethoxylated pentaerythritol with the molecular weight of 600-800 according to the mass ratio of 1:1, a step of; the mass ratio of the compound alcohol to isophorone diisocyanate is 2:3, the mass ratio of the polyurethane prepolymer to the trimethyl hexamethylenediamine is 1: (9-10).
5. The surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin board material, which is characterized in that: in the step (2), the mass ratio of the epoxy resin E-51 to the branched epoxy resin A to the branched epoxy resin B is 3:2:1, a step of; the dosage of the benzyl dimethylamine is 0.3 to 0.4 weight percent of the total amount of the compound resin, and the mass ratio of the compound resin to the curing agent is 3:1.
6. the surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin board material, which is characterized in that: in the step (2), during hot-pressing compounding, the hot-pressing temperature is 130-140 ℃ and the pressure is 5-10 MPa; the coating amount of the glue solution is 150-250 g/m 2 。
7. The surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin board material, which is characterized in that: in the step (2), the glue solution contains fluorinated graphene and graphene oxide, wherein the dosage of the fluorinated graphene is 0.5-0.8 wt% of the total amount of the compound resin, and the dosage of the graphene oxide is 0.8-1 wt% of the total amount of the compound resin;
the surface of the fluorinated graphene and the surface of the oxidized graphene are treated by a silane coupling agent, and the specific steps are as follows: mixing KH-560, methanol and deionized water, performing ultrasonic dispersion for 10-20 min, hydrolyzing at 30-40 ℃ for 20-24 h, adding fluorinated graphene or graphene oxide, reacting for 3-4 h in a water bath at 80-85 ℃, performing centrifugal washing, and performing freeze drying.
8. The surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin board material, which is characterized in that: in the above reaction, the catalyst is dibutyl tin dilaurate.
9. The surface waterproof rubbing process of a mobile phone shell based on a glass fiber epoxy resin board material, which is characterized in that: the epoxy resin is epoxy resin E-44 or epoxy resin E-51.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311114054.6A CN117141015A (en) | 2023-08-31 | 2023-08-31 | Surface waterproof rubbing process of mobile phone shell based on glass fiber epoxy resin plate |
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| CN202311114054.6A CN117141015A (en) | 2023-08-31 | 2023-08-31 | Surface waterproof rubbing process of mobile phone shell based on glass fiber epoxy resin plate |
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