CN111218020A - Preparation method of plastic surface hardening material and plastic surface hardening method - Google Patents
Preparation method of plastic surface hardening material and plastic surface hardening method Download PDFInfo
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- CN111218020A CN111218020A CN201811404944.XA CN201811404944A CN111218020A CN 111218020 A CN111218020 A CN 111218020A CN 201811404944 A CN201811404944 A CN 201811404944A CN 111218020 A CN111218020 A CN 111218020A
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- plastic
- surface hardening
- plastic surface
- polymer resin
- hardening material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention provides a preparation method of a plastic surface hardening material, which comprises the steps of adding 2-6 functional group urethane acrylate oligomer resin into an ester solvent, and stirring for 2-60min to form a transparent dispersion; adding 6-10 functional group-aggregated urethane acrylate high polymer resin into the transparent dispersion, wherein the mass ratio of the oligomer resin to the high polymer resin is 5:1-3, and stirring for reaction for 0.5-3 h; the high polymer resin and the low polymer resin have different numbers of functional groups; and after the reaction is completed, adding an initiator, wherein the addition amount of the initiator is 2-7% of the total amount of the oligomer resin and the high polymer resin, and continuously stirring for reaction for 1-2 hours to obtain the plastic surface hardening material. The preparation method of the plastic surface hardening material and the film layer obtained by the plastic surface hardening method have good bending resistance and are very environment-friendly.
Description
Technical Field
The invention relates to plastic surface treatment, in particular to a preparation method of a plastic surface hardening material and a plastic surface hardening method.
Background
Various electronic devices play a significant role in daily life of people, wherein mobile phones are more indispensable articles, and more than half of people use mobile phones for more than 5 hours every day. Because of the extremely high frequency of use, the mobile phone shell, especially the rear cover, is required to have stronger wear resistance, and simultaneously, the requirement of appearance design is also met. Rear cover materials of electronic equipment are increasingly abundant, and plastics, bamboo wood, ceramics, glass and metal are applied, and among them, engineering plastic materials such as PC (polycarbonate), PMMA (polymethyl methacrylate, acrylic), PC-PMMA composite board, ABS (acrylonitrile-butadiene-styrene plastic) and the like are most widely used due to the advantages of low price, light materials, easy plasticity and the like, and the use range is more than 50%. However, the plastic rear cover is the least wear resistant of all the materials used, and is very susceptible to scratches, which adversely affect the long-term use and the aesthetic appearance of the device.
The method for coating the surface of the plate is one of the methods for solving the problem, common coating material solvents are ketones, benzenes and the like, the product is a two-component or multi-component formula, and a layer of film is formed on the surface of a base material after the product is subjected to ultraviolet light curing in the modes of spraying, curtain coating and the like. However, these materials have several problems: 1. ketone and benzene solvents have carcinogenicity and can cause harm to human health and environment; 2. the more the product components, the more complex the synthesis process, and the poorer the stability of the finished product; 3. the hardness and flexibility of the product after film forming cannot be achieved at the same time, and the application of the product on flexible materials is limited due to poor bending resistance of the film layer.
Disclosure of Invention
The invention mainly solves the technical problem of providing a preparation method of a plastic surface hardening material with better bending resistance of a film layer and environmental protection and a plastic surface hardening method. In order to solve the technical problems, the invention adopts a technical scheme that:
a process for preparing the surface hardening material of plastics includes
Adding 2-6 functional group-aggregated urethane acrylate oligomer resin into an ester solvent, and stirring for 2-60min to form a transparent dispersion;
adding 6-10 functional group urethane acrylate high polymer resin into the transparent dispersion, wherein the mass ratio of the oligomer resin to the high polymer resin is 5:1-3, and stirring for reaction for 0.5-3 h; the high polymer resin and the low polymer resin have different numbers of functional groups;
and after the reaction is completed, adding an initiator, wherein the addition amount of the initiator is 2-7% of the total amount of the oligomer resin and the polymer resin, and continuously stirring for reaction for 1-2h to obtain the plastic surface hardening material.
In one embodiment, the ester solvent is at least one of ethyl acetate, butyl acetate and methyl formate.
In one embodiment, the initiator is at least one of 184, BP, and 1173.
A method of plastic surface hardening comprising:
cleaning the surface of the plastic product;
spraying or curtain-coating the hardened material on the surface of the plastic product;
preheating the sprayed plastic product at 20-70 ℃ for 1-5 min;
placing the preheated plastic product under an ultraviolet curing lamp for curing at normal temperature for 1-3 min;
and cooling to room temperature to obtain the hardened plastic product.
In one embodiment, the plastic article is a PC, PMMA or PMMA/PC composite plate.
In one embodiment, the plastic article is a back cover of an electronic device.
A method of plastic surface hardening comprising:
cleaning the surface of the plastic product;
fixing the plastic product on a clamp of a drawing machine;
after the plastic product is immersed in the plastic surface hardening material, the plastic product is lifted upwards at a speed of 100-100000 mu m/min until the plastic product is completely separated from the plastic surface hardening material;
preheating the plastic product subjected to dip coating at 20-70 ℃ for 1-5 min;
placing the preheated plastic product under an ultraviolet curing lamp for curing at normal temperature for 1-3 min;
and cooling to room temperature to obtain the hardened plastic product.
In one embodiment, the plastic article is a PC, PMMA or PMMA/PC composite plate.
In one embodiment, the plastic article is a back cover of an electronic device.
In the preparation method of the plastic surface hardening material, nontoxic and harmless esters are used as a solvent, and the surface of an optical plastic such as a PC, PMMA or PMMA/PC composite board or a flexible film sheet can be hardened. The coating has good optical property, high crosslinking density, low curing shrinkage rate, extremely high hardness, excellent wear resistance and scrawling resistance and certain antibacterial effect, and is not easy to generate rainbow lines. After film forming, the coating can form firm bonding force with a substrate, so that the coated surface can be protected for a long time, the coating process is simple, and the production efficiency is high. The product is a single component, the preparation process is simple, and the stability of the finished product is high; after film forming, the film layer is resistant to bending, the hardness can be improved by 2-4h compared with other film coating materials, and the curing time is short.
Detailed Description
The invention provides a preparation method of a plastic surface hardening material, which comprises the following steps:
adding 2-6 functional group-aggregated urethane acrylate oligomer resin into an ester solvent, and stirring for 2-60min to form a transparent dispersion;
specifically, in one embodiment, the ester solvent is at least one of ethyl acetate, butyl acetate and methyl formate.
Adding 6-10 functional group urethane acrylate high polymer resin into the transparent dispersion, wherein the mass ratio of the oligomer resin to the high polymer resin is 5:1-3, and stirring for reaction for 0.5-3 h; the high polymer resin and the low polymer resin have different numbers of functional groups.
The preparation method of the plastic surface hardening material comprises two polyurethane acrylate resins with different functional groups, wherein one is polyurethane acrylate oligomer resin, and the other is polyurethane acrylate high polymer resin. Urethane Acrylate (PUA) is a generic name of a high-molecular prepolymer having a urethane (-NHCOO-) bond as a main linking group, and is mainly formed by condensation polymerization of diisocyanate, a long-chain diol, and hydroxy acrylate; the main reaction in the process is that-NCO in diisocyanate and-OH groups in long-chain dihydric alcohol and acrylic hydroxy ester are subjected to nucleophilic addition reaction under the conditions of catalyst and heating. A variety of PUA prepolymers having different functionalities and different properties can be synthesized. The 2-6 functional group urethane acrylate oligomer resin mainly provides toughness, the 6-10 functional group urethane acrylate high polymer resin provides hardness, and multiple hydrogen bonds can be formed among high polymer molecular chains, so that the polyurethane film has excellent hardness, mechanical wear resistance and flexibility. The formula does not use monomers, can effectively reduce the shrinkage of the coating, reduce the internal stress during curing, increase the adhesive force of the coating to the surface of the plastic and improve the flexibility of a coating film. When the proportion of the soft resin and the hard resin is reduced, the hardness of the coating film is gradually increased, and the wear resistance is improved.
And after the reaction is completed, adding an initiator, wherein the addition amount of the initiator is 2-7% of the total amount of the oligomer resin and the high polymer resin, and continuously stirring for reaction for 1-2h to obtain the plastic surface hardening material.
The urethane acrylate system is mainly composed of urethane groups with hard segment characteristics and long aliphatic chains with soft segment properties.
Specifically, in one embodiment, a method of plastic surface hardening includes:
cleaning the surface of the plastic product;
spraying or curtain-coating the hardened material on the surface of the plastic product;
preheating the sprayed plastic product at 20-70 ℃ for 1-5 min;
placing the preheated plastic product under an ultraviolet curing lamp for curing at normal temperature for 1-3 min;
and cooling to room temperature to obtain the hardened plastic product.
In one embodiment, the plastic article is a PC, PMMA or PMMA/PC composite plate.
In one embodiment, the plastic article is a back cover of an electronic device.
A method of plastic surface hardening comprising:
cleaning the surface of the plastic product;
fixing the plastic product on a clamp of a drawing machine;
after the plastic product is immersed in the plastic surface hardening material, the plastic product is lifted upwards at a speed of 100-100000 mu m/min until the plastic product is completely separated from the plastic surface hardening material;
preheating the plastic product subjected to dip coating at 20-70 ℃ for 1-5 min;
placing the preheated plastic product under an ultraviolet curing lamp for curing at normal temperature for 1-3 min;
and cooling to room temperature to obtain the hardened plastic product.
In one embodiment, the plastic article is a PC, PMMA or PMMA/PC composite plate.
In one embodiment, the plastic article is a back cover of an electronic device.
In the preparation method of the plastic surface hardening material, nontoxic and harmless esters are used as a solvent, and the surface of an optical plastic such as a PC, PMMA or PMMA/PC composite board or a flexible film sheet can be hardened. The coating has good optical property, high crosslinking density, low curing shrinkage rate, extremely high hardness, excellent wear resistance and scrawling resistance and certain antibacterial effect, and is not easy to generate rainbow lines. After film forming, the coating can form firm bonding force with a substrate, so that the coated surface can be protected for a long time, the coating process is simple, and the production efficiency is high. The product is a single component, the preparation process is simple, and the stability of the finished product is high; after film forming, the film layer is resistant to bending, the hardness can be improved by 2-4h compared with other film coating materials, and the curing time is short.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, or direct or indirect applications in other related fields, which are made by the contents of the present specification, are included in the scope of the present invention.
Claims (9)
1. A method for preparing a plastic surface hardening material is characterized by comprising
Adding 2-6 functional group-aggregated urethane acrylate oligomer resin into an ester solvent, and stirring for 2-60min to form a transparent dispersion;
adding 6-10 functional group-aggregated urethane acrylate high polymer resin into the transparent dispersion, wherein the mass ratio of the oligomer resin to the high polymer resin is 5:1-3, and stirring for reaction for 0.5-3 h; the high polymer resin and the low polymer resin have different numbers of functional groups;
and after the reaction is completed, adding an initiator, wherein the addition amount of the initiator is 2-7% of the total amount of the oligomer resin and the high polymer resin, and continuously stirring for reaction for 1-2 hours to obtain the plastic surface hardening material.
2. The method for preparing a plastic surface-hardening material according to claim 1, wherein the ester solvent is at least one of ethyl acetate, butyl acetate, and methyl formate.
3. The method for preparing a plastic surface-hardening material according to claim 1, wherein the initiator is at least one of 184, BP, and 1173.
4. A method of plastic surface hardening comprising:
cleaning the surface of the plastic product;
spraying or curtain coating the plastic surface hardening material of any one of claims 1 to 3 on the surface of the plastic product;
preheating the sprayed plastic product at 20-70 ℃ for 1-5 min;
placing the preheated plastic product under an ultraviolet curing lamp for curing at normal temperature for 1-3 min;
and cooling to room temperature to obtain the hardened plastic product.
5. A method of surface hardening a plastic according to claim 4, wherein said plastic is PC, PMMA or PMMA/PC composite.
6. A method of plastic surface hardening according to claim 5, wherein the plastic article is a back cover of an electronic device.
7. A method of plastic surface hardening comprising:
cleaning the surface of the plastic product;
fixing the plastic product on a clamp of a drawing machine;
after the plastic product is immersed in the plastic surface hardening material of any one of claims 1 to 3, the plastic product is pulled upwards at a speed of 100-100000 μm/min until completely leaving the plastic surface hardening material;
preheating the plastic product subjected to dip coating at 20-70 ℃ for 1-5 min;
placing the preheated plastic product under an ultraviolet curing lamp for curing at normal temperature for 1-3 min;
and cooling to room temperature to obtain the hardened plastic product.
8. A method of surface hardening a plastic according to claim 7, wherein said plastic is PC, PMMA or PMMA/PC composite.
9. The method of plastic surface hardening of claim 8, wherein the plastic article is a back cover of an electronic device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811404944.XA CN111218020A (en) | 2018-11-23 | 2018-11-23 | Preparation method of plastic surface hardening material and plastic surface hardening method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811404944.XA CN111218020A (en) | 2018-11-23 | 2018-11-23 | Preparation method of plastic surface hardening material and plastic surface hardening method |
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| CN111218020A true CN111218020A (en) | 2020-06-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811404944.XA Pending CN111218020A (en) | 2018-11-23 | 2018-11-23 | Preparation method of plastic surface hardening material and plastic surface hardening method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120276373A1 (en) * | 2011-04-27 | 2012-11-01 | Port Anthony B | Weather Resistant Exterior Film Composite |
| CN104199128A (en) * | 2014-08-21 | 2014-12-10 | 昆山乐凯锦富光电科技有限公司 | Optical hardening film |
| CN106752861A (en) * | 2016-12-02 | 2017-05-31 | 东莞市惠尔明高分子材料科技有限公司 | One kind is resistance to fall optical curing of UV coating and preparation method thereof |
-
2018
- 2018-11-23 CN CN201811404944.XA patent/CN111218020A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120276373A1 (en) * | 2011-04-27 | 2012-11-01 | Port Anthony B | Weather Resistant Exterior Film Composite |
| CN104199128A (en) * | 2014-08-21 | 2014-12-10 | 昆山乐凯锦富光电科技有限公司 | Optical hardening film |
| CN106752861A (en) * | 2016-12-02 | 2017-05-31 | 东莞市惠尔明高分子材料科技有限公司 | One kind is resistance to fall optical curing of UV coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李肇强: "《现代涂料的生产及应用 第2版》", 31 March 2017, 上海：上海科学技术文献出版社 * |
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Application publication date: 20200602 |