CN109554106B - Hyperbranched polyurethane acrylate hardened coating and preparation method thereof - Google Patents
Hyperbranched polyurethane acrylate hardened coating and preparation method thereof Download PDFInfo
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- CN109554106B CN109554106B CN201811420277.4A CN201811420277A CN109554106B CN 109554106 B CN109554106 B CN 109554106B CN 201811420277 A CN201811420277 A CN 201811420277A CN 109554106 B CN109554106 B CN 109554106B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- 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
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- 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
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Abstract
The invention discloses a hyperbranched polyurethane acrylate hardened coating and a preparation method thereof. The hardened coating mainly comprises a hyperbranched polyurethane acrylate oligomer with double bonds at the tail end and a hexa-functionality polyurethane acrylate oligomer, wherein the hyperbranched polyurethane acrylate oligomer accounts for 5-20 parts by mass, and the hexa-functionality polyurethane acrylate oligomer accounts for 25-50 parts by mass; the polyurethane acrylate dendritic oligomer with double bonds at the tail end contains rigid triazine carbon nitrogen heterocycle, so that the hardness of the coating is improved. The preparation method is simple, the hardened coating has excellent mechanical properties under the condition of low HBPUA content, has the characteristics of high hardness, yellowing resistance and the like, and the mechanical properties of the hardened coating can be regulated and controlled by changing the addition amount of the HBPUA.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a hyperbranched polyurethane acrylate hardened coating and a preparation method thereof.
Background
With the opening of the preface screen in the 5G period, the mobile phone terminal will be changed once again, and higher requirements are provided for the signal transmission capability of the mobile phone shell. For the traditional metal back cover plate, the attenuation of the traditional metal back cover plate to 5G high-frequency band signals is serious, so that the rear cover of the 5G mobile phone cannot be made of metal. The handset back cover plate will be predominantly plastic, in view of cost.
However, the plastic has low surface hardness, poor wear resistance and easy scratch generation, which limits the application of the plastic in the back cover plate of the mobile phone. It is important to coat the surface of the plastic with a transparent hardening film to improve its mechanical properties. The method has low cost, and is simple and easy to operate. In view of the excellent weatherability, flexibility and various controllable characteristics of polyurethane propionate, polyurethane acrylate can be selected as a film forming material for hard films.
However, urethane acrylate contains a small amount of photosensitive groups, which results in that the hardness of the hard coat film after photocuring is not satisfactory due to low crosslinking density. This requires structural modification to the film in order to increase its cured film hardness.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a hyperbranched polyurethane acrylate hardened coating and a preparation method thereof.
Hyperbranched polyurethane acrylate hardened coating
The hardened coating mainly comprises 5-20 parts by mass of hyperbranched polyurethane acrylate oligomer (HBPUA) and 25-50 parts by mass of hexa-functionality polyurethane acrylate oligomer (PUA-6 ene).
The molecular formula of the hyperbranched polyurethane acrylate oligomer (HBPUA) with the double bond at the tail end is as follows:
in the above structure, the end-capping agent of the hyperbranched urethane acrylate oligomer (HBPUA) is di-functional trimethylolpropane diallyl ether.
The formula of the hexafunctional urethane acrylate oligomer (PUA-6ene) is as follows:
the hardened coating further comprises a reactive diluent, a UV curing photoinitiator and an inactive diluent, wherein the reactive diluent is 4-6 parts by weight, the UV curing photoinitiator is 2-3 parts by weight, and the inactive diluent is 40-60 parts by weight.
The non-reactive diluent adopts ethanol and isopropanol.
The reactive diluent adopts pentaerythritol tetra-mercapto acetate or pentaerythritol tetra (3-mercaptopropionic acid) ester (PETMP).
Secondly, the preparation method of the hyperbranched polyurethane acrylate hardened coating comprises the following steps:
1) dissolving hyperbranched polyurethane acrylate oligomer (HBPUA), hexa-functionality polyurethane acrylate oligomer (PUA-6ene), reactive diluent and UV curing photoinitiator in non-reactive diluent, and fully mixing to obtain a coating;
2) coating the coating on the surface of a PC (polycarbonate) substrate pretreated by acid, alkali and alcohol by adopting a dip-coating or spraying mode, and naturally leveling the coating to obtain the PC substrate coated with the coating;
3) and (3) drying the PC substrate coated with the coating, and carrying out ultraviolet light initiated curing on the PC substrate by using a mercury lamp to obtain the hyperbranched polyurethane acrylate hardened coating.
The drying temperature in the step 3) is 60 ℃, and the drying time is 5 min.
In the step 3), the ultraviolet light initiated curing conditions are as follows: mercury lamp power P is 1kw, mercury lamp wavelength λ is 365nm, and illumination time is 30 s.
In the step 1), the UV curing photoinitiator is a mixture of the photoinitiator 184 and the photoinitiator TPO.
The ratio of the photoinitiator 184 to the photoinitiator TPO is 4: 1.
The non-reactive diluent adopts ethanol and isopropanol.
The reactive diluent adopts pentaerythritol tetra-mercapto acetate or pentaerythritol tetra (3-mercaptopropionic acid) ester (PETMP).
The preparation method of the hyperbranched polyurethane acrylate oligomer (HBPUA) comprises the following steps:
1.1) adding triallyl cyanurate (TAC), thioglycerol (MTGL) and a photoinitiator into a beaker, heating and dissolving to obtain a mixed solution, irradiating the mixed solution with ultraviolet light at normal temperature, dissolving the irradiated mixed solution in ethanol, and precipitating the mixed solution in petroleum ether for multiple times to obtain a clear viscous liquid (TAC-MTGL);
1.2) adding isophorone diisocyanate, dibutyltin dilaurate, hydroquinone and tetrahydrofuran into a reaction vessel provided with a condenser pipe, a magnetic stirrer and a nitrogen inlet, continuously and slowly dropwise adding a mixed solution of tetrahydrofuran and trimethylolpropane diallyl ether into the reaction vessel at 50 ℃ for continuous reaction, and then heating the solution to 60 ℃;
1.3) adding a clear mixed solution of viscous liquid (TAC-MTGL) and tetrahydrofuran into the reaction container in the step 2) and stirring to obtain a crude product, and precipitating the crude product in cyclohexane/diethyl ether for multiple times to obtain a white solid product, namely the hyperbranched polyurethane acrylate oligomer (HBPUA).
In step 1.1) of the preparation method of the hyperbranched urethane acrylate oligomer (HBPUA), the photoinitiator is 2959, and the irradiation conditions of the mixed solution at normal temperature are as follows: the mixture was irradiated with 365nm light for 1 h.
In step 1.2) of the preparation method of the hyperbranched urethane acrylate oligomer (HBPUA), the mass fraction ratio of dibutyltin dilaurate to hydroquinone is 2: 1.
the HBPUA contains a large number of double bonds, so that the functionality is increased, the crosslinking density can be improved, and the photocuring time is shortened. Furthermore, HBPUA contains rigid triazine carbon nitrogen heterocycles, which further increase the hardness of the coating. Meanwhile, the low viscosity characteristic of the hyperbranched product is utilized, the viscosity of the system is reduced, and the leveling of the coating is facilitated. In addition, the PUA-6ene structurally contains flexible fatty chains, so that the coating achieves high hardness and has good toughness. Moreover, HBPUA and PUA-6ene do not contain benzene ring groups, the coating is not easy to yellow, and the coating has excellent mechanical properties under the condition of low HBPUA content and has the characteristics of high hardness, yellow stain resistance and the like.
The invention has the following beneficial effects:
1. the hyperbranched polyurethane acrylate hardened coating is prepared by ultraviolet curing, the preparation method is simple, and the mechanical property of the hardened coating can be regulated and controlled by changing the addition amount of HBPUA;
2. the obtained hardened coating has excellent mechanical properties under the condition of low HBPUA content, and has the characteristics of high hardness, yellowing resistance and the like.
Drawings
FIG. 1 is a schematic diagram of TAC-MTGL of the example1H NMR spectrum.
FIG. 2 shows HBPUA of the example1H NMR spectrum.
Detailed Description
The present invention will be described in more detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
The examples of the invention are as follows:
the hyperbranched urethane acrylate oligomer (HBPUA) used in the following examples was prepared by the following procedure:
to a 50mL beaker was added 4.98g of triallyl cyanurate (TAC), 8.10g of thioglycerol (MTGL) and 14.3mg of photoinitiator 2954. The reaction in the beaker was heated slightly to dissolve the photoinitiator 2954, then mixed well and irradiated with 365nm light for 1h at normal temperature. Subsequently, it was dissolved in 30mL of ethanol and precipitated three times in 200mL of petroleum ether to obtain a clear viscous liquid (TAC-MTGL). FIG. 1 shows TAC-MTGL1H NMR spectrum.
To a 100mL three-necked flask equipped with a condenser, a magnetic stirrer, and a nitrogen inlet was added 8.89g of isophorone diisocyanate, 0.5 wt% of dibutyltin dilaurate, 0.25 wt% of hydroquinone, and 5mL of tetrahydrofuran. Subsequently, a mixed solution of 10mL of tetrahydrofuran and 8.56g of trimethylolpropane diallyl ether was slowly added dropwise to the reaction flask at 50 ℃ for 1.5 hours. After further reaction at 50 ℃ for 4.5h, the solution was heated to 60 ℃. Then, a mixed solution of 3.73g TAC-MTGL and 10mL tetrahydrofuran was added to the above reaction vessel and stirred at 60 ℃ for 6 hours. Finally, the crude product was precipitated twice in 400mL of cyclohexane/diethyl ether (V1: V2 ═ 9: 1) to yield the product HBPUA as a white solid. FIG. 2 shows HBPUA1H NMR spectrum.
Example 1:
1) 0.5g of HBPUA described in example 1, 8.5g of PUA-6ene, and 1.0g of pentaerythritol tetrakis (3-mercaptopropionate) were dissolved in 9.5g of isopropyl alcohol, and 0.4g of photoinitiator 184 and 0.1g of photoinitiator TPO were added thereto, followed by ultrasonic dissolution to obtain a precoating liquid.
2) And spraying the pre-coating solution on the surface of the PC substrate pretreated by alcohol and acid and alkali, and naturally leveling the coating to obtain the PC substrate coated with the coating.
3) The PC substrate coated with the coating was left to bake at 60 ℃ for 5min and then cured under a mercury lamp for 30s to give a hard coat layer having a film thickness of about 30 μm.
The pencil hardness of the coatings was determined using the ASTM D3363 coating hardness Standard test method, and the hardcoated pencil hardness obtained in example 1 was 3H.
Example 2:
1) 1.5g of HBPUA described in example 1, 7.5g of PUA-6ene, and 1.0g of pentaerythritol tetrakis (3-mercaptopropionate) were dissolved in 9.5g of isopropyl alcohol, and 0.4g of photoinitiator 184 and 0.1g of photoinitiator TPO were added thereto, followed by ultrasonic dissolution to obtain a precoating liquid.
2) And spraying the pre-coating solution on the surface of the PC substrate pretreated by alcohol and acid and alkali, and naturally leveling the coating to obtain the PC substrate coated with the coating.
3) The PC substrate coated with the coating was left to bake at 60 ℃ for 5min and then cured under a mercury lamp for 30s to give a hard coat layer having a film thickness of about 30 μm.
The pencil hardness of the coatings was measured using the ASTM D3363 Standard test method for film hardness, and the pencil hardness of the hardcoat prepared in example 2 was 4H.
Example 3:
1) 2.5g of HBPUA described in example 1, 6.5g of PUA-6ene, and 1.0g of pentaerythritol tetrakis (3-mercaptopropionate) were dissolved in 9.5g of isopropyl alcohol, and 0.4g of photoinitiator 184 and 0.1g of photoinitiator TPO were added thereto, followed by ultrasonic dissolution to obtain a precoating liquid.
2) And spraying the pre-coating solution on the surface of the PC substrate pretreated by alcohol and acid and alkali, and naturally leveling the coating to obtain the PC substrate coated with the coating.
3) The PC substrate coated with the coating was left to bake at 60 ℃ for 5min and then cured under a mercury lamp for 30s to give a hard coat layer having a film thickness of about 30 μm.
The pencil hardness of the coatings was determined using the ASTM D3363 coating hardness Standard test method, and the hardcoated pencil hardness obtained in example 3 was 5H.
The PC (polycarbonate sheet) substrates of the various examples were pretreated with acid base and alcohol using the following procedure: soaking the cut PC substrate (3cm multiplied by 3cm) in hydrochloric acid solution with the pH value of 3, and ultrasonically cleaning for 5 min; then soaking the mixture in a sodium hydroxide solution with the pH value of 11, and ultrasonically cleaning for 5 min; and then ultrasonically cleaning the substrate for 5min by using deionized water, and finally ultrasonically cleaning the substrate for 5min by using isopropanol to obtain the PC substrate pretreated by alcohol and acid-base.
From the test results of the above examples, the invention can have excellent mechanical properties at low HBPUA content, and has the characteristics of higher hardness, yellowing resistance and the like, and the mechanical properties of the hardened coating can be regulated and controlled by changing the addition amount of the HBPUA, and the hardness of the hardened coating is higher as the addition amount of the HBPUA is larger. The hyperbranched polyurethane acrylate oligomer and the hexa-functionality polyurethane acrylate are selected, and the hardened coating with excellent mechanical property is obtained through ultraviolet light curing, so that the application of the hyperbranched polyurethane acrylate hardened coating in the aspects of mobile phone back cover plates, other electronic products and the like is realized.
Claims (9)
1. A hyperbranched polyurethane acrylate hardened coating is characterized in that:
the hardened coating mainly comprises a hyperbranched polyurethane acrylate oligomer with a double bond at the tail end and a hexa-functionality polyurethane acrylate oligomer, wherein the hyperbranched polyurethane acrylate oligomer accounts for 5-20 parts by weight, and the hexa-functionality polyurethane acrylate oligomer accounts for 25-50 parts by weight;
the molecular formula of the hyperbranched polyurethane acrylate oligomer with the double bond at the tail end is as follows:
the hexafunctional urethane acrylate oligomer has the following molecular formula:
2. the hyperbranched urethane acrylate hardcoat of claim 1 wherein:
the hardened coating further comprises an active diluent, a UV curing photoinitiator and an inactive diluent, wherein the active diluent is 4-6 parts by weight, the UV curing photoinitiator is 2-3 parts by weight, and the inactive diluent is 40-60 parts by weight.
3. The hyperbranched urethane acrylate hardcoat of claim 2 wherein:
the reactive diluent adopts pentaerythritol tetra-mercaptoacetate or pentaerythritol tetra (3-mercaptopropionic acid) ester.
4. A process for the preparation of a hyperbranched urethane acrylate hard-coat layer according to any of claims 1 to 3, characterized in that it comprises the following steps:
1) dissolving hyperbranched polyurethane acrylate oligomer, hexa-functionality polyurethane acrylate oligomer, reactive diluent and UV curing photoinitiator in non-reactive diluent, and fully mixing to obtain a coating;
2) coating the coating on the surface of the PC substrate pretreated by acid, alkali and alcohol in a dip-coating or spraying manner, and naturally leveling the coating to obtain the PC substrate coated with the coating;
3) and (3) drying the PC substrate coated with the coating, and carrying out ultraviolet light initiated curing on the PC substrate by using a mercury lamp to obtain the hyperbranched polyurethane acrylate hardened coating.
5. The method of preparing a hyperbranched urethane acrylate hard-coat layer according to claim 4, wherein: the drying temperature in the step 3) is 60 ℃, and the drying time is 5 min.
6. The method of preparing a hyperbranched urethane acrylate hard-coat layer according to claim 4, wherein: in the step 3), the ultraviolet light initiated curing conditions are as follows: mercury lamp power P is 1kw, mercury lamp wavelength λ is 365nm, and illumination time is 30 s.
7. The method of preparing a hyperbranched urethane acrylate hard-coat layer according to claim 4, wherein: in the step 1), the UV curing photoinitiator is a mixture of a photoinitiator 184 and a photoinitiator TPO; the mass ratio of the photoinitiator 184 to the photoinitiator TPO is 4: 1.
8. The method of preparing a hyperbranched urethane acrylate hard-coat layer according to claim 4, wherein: the preparation method of the hyperbranched polyurethane acrylate oligomer comprises the following steps:
1.1) adding triallyl cyanurate, thioglycerol and a photoinitiator into a beaker, heating and dissolving to obtain a mixed solution, irradiating the mixed solution with ultraviolet light at normal temperature, dissolving the irradiated mixed solution in ethanol, and precipitating the mixed solution in petroleum ether for multiple times to obtain a clear viscous liquid;
1.2) adding isophorone diisocyanate, dibutyltin dilaurate, hydroquinone and tetrahydrofuran into a reaction vessel provided with a condenser pipe, a magnetic stirrer and a nitrogen inlet, continuously and slowly dropwise adding a mixed solution of tetrahydrofuran and trimethylolpropane diallyl ether into the reaction vessel at 50 ℃ for continuous reaction, and then heating the solution to 60 ℃;
1.3) adding a clear mixed solution of viscous liquid and tetrahydrofuran into the reaction container in the step 1.2), stirring to obtain a crude product, and precipitating the crude product in cyclohexane or diethyl ether for multiple times to obtain a white solid product, namely the hyperbranched polyurethane acrylate oligomer.
9. The method of preparing a hyperbranched urethane acrylate hard-coat layer according to claim 8, wherein: in the step 1.1), the photoinitiator is a photoinitiator 2959, and the irradiation conditions of the mixed solution at normal temperature are as follows: the mixture was irradiated with 365nm light for 1 h.
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| CN111518467A (en) * | 2020-03-27 | 2020-08-11 | 浙江大学 | Preparation method of high-functionality polyurethane acrylate-silicon dioxide composite hardened coating |
| CN115477781B (en) * | 2021-06-16 | 2023-07-25 | 宁波安特弗新材料科技有限公司 | Hard coating film for folding screen and preparation method thereof |
| CN117903394A (en) * | 2024-03-20 | 2024-04-19 | 江苏瑞洋安泰新材料科技有限公司 | Bio-based isocyanate crosslinking agent and preparation process thereof |
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