CN113817402A - Dual-curing highlight black automobile interior coating and preparation method thereof - Google Patents

Dual-curing highlight black automobile interior coating and preparation method thereof Download PDF

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CN113817402A
CN113817402A CN202110848377.2A CN202110848377A CN113817402A CN 113817402 A CN113817402 A CN 113817402A CN 202110848377 A CN202110848377 A CN 202110848377A CN 113817402 A CN113817402 A CN 113817402A
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dual
curing
interior coating
polyurethane resin
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CN113817402B (en
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彭健华
蒋卫华
吴勇
冯敏乐
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Guangdong Xigui UV Curing Materials Co Ltd
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Guangdong Xigui UV Curing Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds

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  • Application Of Or Painting With Fluid Materials (AREA)
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Abstract

The invention belongs to the technical field of coatings, and particularly relates to a dual-curing highlight black automobile interior coating and a preparation method thereof, wherein the dual-curing highlight black automobile interior coating comprises the following components in percentage by weight: 15-25% of polyurethane resin, 35-55% of dual-curing UV resin, 3-7% of active monomer, 2-4% of photoinitiator, 0.3-0.8% of auxiliary agent, 3-5% of nano black paste and the balance of solvent. The dual-curing highlight black automobile interior coating is characterized in that a UV resin capable of being cured thermally is introduced into a system aiming at a workpiece with a complex shape, and the UV resin can still be dried and cured without the irradiation of UV rays.

Description

Dual-curing highlight black automobile interior coating and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a dual-curing highlight black automobile interior coating and a preparation method thereof.
Background
The plastic automotive interior part comprises main decorative parts such as a central control part, a door handle, a gear plate and the like, and has high requirements on weather resistance, heat resistance and appearance, the conventional process is produced by spraying two-component PU paint, and the PU paint is characterized by being baked and dried, is suitable for a three-dimensional workpiece with a complex shape, has the characteristics of good luster and leveling property, bright color and the like, but has the defects of low hardness, relatively poor chemical resistance, long curing time and the like.
Chinese patent document CN 109280478A discloses the use of UV paint for automobile interior decorationThe method comprises the following steps: s1, uniformly blending the UV coating, the UV curing agent and the UV coating diluent according to the weight ratio of 5: 1: 2-3, spraying the mixture on a plain material layer, leveling and drying at normal temperature for 5-10min, and then keeping the mixture at the temperature of 60-80 ℃ for 5-15 min; s2, carrying out UV curing, wherein the UV exposure energy is 1200-1800MJ/cm2. Although the UV curing speed is faster and the crosslinking density is higher than that of a heat-drying coating, for automobile interior parts with complex structures, sufficient irradiation is difficult to realize in the UV curing process, and complete curing of the coating cannot be well ensured.
In view of the above, there is a need to develop a dual-curable automotive interior coating, which ensures sufficient curing, ensures curing speed as much as possible, improves production efficiency, and enables the coating to have the characteristics of high curing speed, high hardness, good fullness, good chemical resistance and the like of the UV coating.
Disclosure of Invention
In order to solve the problems, the invention discloses a dual-curing highlight black automobile interior coating and a preparation method thereof, aiming at workpieces with complex shapes, the dual-curing highlight black automobile interior coating introduces a thermocurable UV resin into a system, can still be dried and cured under the irradiation of no UV rays, and has the characteristics of high curing speed, high hardness, good fullness, good chemical resistance and the like because of the fact that the dual-curing highlight black automobile interior coating is the UV coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
the dual-curing highlight black automobile interior coating comprises the following components in percentage by weight:
Figure BDA0003181549830000011
Figure BDA0003181549830000021
preferably, the polyurethane resin is a mixture of a 6-functional polyurethane resin and a 2-functional polyurethane resin, and the mass ratio of the 6-functional polyurethane resin to the 2-functional polyurethane resin is 3-4: 1.
Preferably, the 6-functional polyurethane resin is 6-functional aliphatic polyurethane acrylate, and the 2-functional polyurethane resin is one or two of 2-functional macromolecular aliphatic polyurethane acrylate and 2-functional polycarbonate polyurethane.
Preferably, the 2-functional polyurethane resin is a 2-functional polycarbonate polyurethane.
Preferably, the mass ratio of the polyurethane resin to the dual curing UV resin is 1: 2-4.
Preferably, the dual-curing UV resin is one or more of L-8464, L-8468 and UA-7706H;
the active monomer is one or more of hydroxyethyl methacrylate (HEMA), tetrahydrofuran acrylate (THFA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), 1, 6-hexanediol diacrylate (HDDA), hydroxymethyl propane triacrylate (TMPTA) and pentaerythritol triacrylate (PET 3A).
Preferably, the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), a-dimethoxy acetophenone (651), 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and Isopropyl Thioxanthone (ITX);
the auxiliary agent is one or more of pure acrylate, polyester modified organic siloxane and polyether modified organic siloxane;
the solvent is one or more of ethyl acetate, isobutyl isobutyrate, isopropanol, isobutanol, butyl acetate, propylene glycol methyl ether acetate and propylene glycol methyl ether.
Preferably, the preparation method of the nano black paste comprises the following steps:
(1) adding 57 mass percent of PMA and 23 mass percent of EFKA4310 into a stirring cylinder, stirring until the PMA and the EFKA are completely dissolved, and then adding 20 mass percent of RAVEN 5000UII into the stirring cylinder;
(2) stirring at a high speed of 800r/min for 30min, standing for 24h, and soaking for moistening;
(3) stirring for 30min at 500r/min, pumping into a horizontal sand mill for grinding after uniform stirring until the fineness is below 5 μm, and obtaining the nano black paste.
Preferably, the grinding conditions in the step (3) are as follows: the grinding pressure was 0.2Pa and the grinding temperature was 60 ℃.
A preparation method of a dual-curing highlight black automobile interior coating comprises the following steps: under the environment of completely isolating ultraviolet light by using a yellow light lamp, uniformly stirring 10% of solvent and nano black slurry, sequentially adding an active monomer, a photoinitiator and the rest solvent, uniformly stirring at the speed of 200r/min, sequentially adding dual-curing UV resin, polyurethane resin and an auxiliary agent, and stirring at the speed of 800r/min for 20min to prepare the dual-curing highlight black automobile coating.
The invention has the following beneficial effects:
(1) the dual-curing highlight black automobile interior coating is characterized in that a thermocurable UV resin is introduced into a system aiming at a workpiece with a complex shape, and the dual-curing highlight black automobile interior coating can still be dried and cured under the irradiation of no UV rays, and has the characteristics of high curing speed, high hardness, good fullness, good chemical resistance and the like due to the fact that the dual-curing highlight black automobile interior coating is a UV coating essentially;
(2) the polyurethane resin in the dual-curing highlight black automotive interior coating adopts 6-functional polyurethane resin and 2-functional polyurethane resin in a matching way, wherein the mass ratio of the 6-functional polyurethane resin to the 2-functional polyurethane resin is 3-4:1, so that the coating is ensured to have higher hardness and good flexibility, and the 2-functional polyurethane resin can help to reduce the system shrinkage and improve the weather resistance of the coating;
(3) the mass ratio of the polyurethane resin to the dual-curing UV resin in the dual-curing highlight black automotive interior coating is 1:2-4, so that the thermosetting effect can be ensured, the thermosetting quality can be ensured under the condition that effective photocuring cannot be carried out due to the complex structure of a workpiece, the complete curing of a coating is ensured, and the property of the coating is further ensured;
(4) the 2-functional polyurethane resin in the dual-curing highlight black automobile interior coating adopts 2-functional polycarbonate polyurethane, so that the viscosity of a coating system can be effectively reduced, the construction is facilitated, the better substrate wettability and the better leveling effect are favorably obtained, and the coating quality is improved.
Detailed Description
The present invention will now be described in further detail with reference to examples.
The preparation method of the nano black paste comprises the following steps:
(1) adding 57 mass percent of PMA and 23 mass percent of EFKA4310 into a stirring cylinder, stirring until the PMA and the EFKA are completely dissolved, and then adding 20 mass percent of RAVEN 5000UII into the stirring cylinder;
(2) stirring at a high speed of 800r/min for 30min, standing for 24h, and soaking for moistening;
(3) stirring for 30min at 500r/min, pumping into a horizontal sand mill for grinding after uniform stirring until the fineness is below 5 μm, and obtaining the nano black paste.
The grinding conditions in the step (3) are as follows: the grinding pressure was 0.2Pa and the grinding temperature was 60 ℃.
The 6-functional aliphatic polyurethane acrylate used in the invention is selected from 6145-100 (Taiwan Changxing), 6147 (Taiwan Changxing) and 1290N (
Figure BDA0003181549830000032
1290N); the 2-functional macromolecular aliphatic urethane acrylate is selected from U-CURE 9300 (molecular weight of 18000); the 2-functional polycarbonate polyurethane is selected from L-6280 (Korotkoff, Guangdong); the dual-curing UV resin is selected from L-8464 (Cochler guangdonglan), L-8468 (Cochler guangdonglan), and UA-7706H (Jiuwei trade in Guangzhou).
Examples 1-6 and comparative examples 1-4 the components and weight percentages thereof used to prepare the dual-cure high gloss black automotive interior coating are shown in table 1.
TABLE 1
Figure BDA0003181549830000031
Figure BDA0003181549830000041
The dual-curing highlight black automotive interior coating prepared by the above example and comparative example formulations comprises the following steps: under the environment of completely isolating ultraviolet light by using a yellow light lamp, uniformly stirring 10% of solvent and nano black slurry, sequentially adding an active monomer, a photoinitiator and the rest solvent, uniformly stirring at the speed of 200r/min, sequentially adding dual-curing UV resin, polyurethane resin and an auxiliary agent, and stirring at the speed of 800r/min for 20min to prepare the dual-curing highlight black automobile coating.
Construction conditions are as follows: substrate pretreatment (flushing, oil removal, drying and electrostatic dust removal) → spraying dual-curing high gloss black (curing agent: coating: 1: 4, spraying film thickness 15-20 μm) → infrared leveling (50 ℃, leveling 3-5min) → UV curing (curing energy 500 mJ/cm)2-600mJ/cm2) → post-bake curing (80 ℃, 8-10min) → off-line of the workpiece.
The coatings obtained in examples 1 to 6 and comparative examples 1 to 4 were subjected to various performance tests, and the test results are shown in Table 2.
TABLE 2
Figure BDA0003181549830000042
Figure BDA0003181549830000051
Construction performance: since the 2-functional polyurethane resins in example 6 and comparative examples 2 to 3 are both 2-functional polycarbonate polyurethane and the 2-functional polycarbonate polyurethane is used in an appropriate amount, the coating materials prepared in example 6 and comparative examples 2 to 3 have better atomization effect and better wettability to the primer material when sprayed and can rapidly achieve mirror leveling after spraying, compared with examples 1 to 5, comparative example 1 and comparative example 4.
To study the curing effect of the coatings prepared in examples 1 to 6 and comparative examples 1 to 4, the plastic part of the door handle workpiece was sprayed and cured under the same curing conditions (50 ℃ IR leveling 5min → UV curing (curing energy 550 mJ/cm)2) → post bake cure (80 c,10min)), it was found that the door handle piece coated with the coating of comparative example 3 was not completely cured at the corners and the bottom, and that the door handle piece coated with the coatings of the remaining comparative examples and examples was completely cured at all portions.
The test method of the wear resistance comprises the following steps: a sample plate with the specification of 10cm multiplied by 10cm is manufactured and placed on a Taber 5135 rotary abrasion-resistant testing machine for testing, and the testing conditions are as follows: the load is 500g, a CS-10F grinding wheel is used for rotating 100 times, the gloss before and after the comparison test is carried out, and the gloss retention rate is more than or equal to 80 percent, so that the product is qualified.
The testing method of the artificial sweat resistance liquid comprises the following steps: artificial sweat composition: 1.07% of ammonia water, 0.48% of sodium chloride and 98.45% of water. The test method comprises the following steps: soaking a piece of clean cotton cloth capable of wrapping the product in prepared hand sweat, sticking the soaked cotton cloth on the paint spraying surface of the product, sealing the product in a self-sealing bag, and standing and storing at 25 ℃. After 24H, the film was taken out and wiped clean with a clean cotton cloth and left at room temperature for 2 hours, and then the appearance was observed.
The test method of the sunscreen cream comprises the following steps: the surface of a sample is wiped clean by using dust-free cloth, sunscreen cream (SPF value is 15) is coated on the surface (thin layer) of the sample, and then the sample is placed in a constant temperature and humidity box (temperature is 55 +/-2 ℃, and relative humidity is 95 +/-2%). After 24 hours, the surface sunscreen cream is taken out and wiped clean, and the sunscreen cream is placed at room temperature for 2 hours and then the appearance of the sunscreen cream is observed.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. The dual-curing highlight black automobile interior coating is characterized by comprising the following components in parts by weight: comprises the following components in percentage by weight:
Figure FDA0003181549820000011
2. the dual cure high gloss black automotive interior coating of claim 1, wherein: the polyurethane resin is a mixture of 6-functional polyurethane resin and 2-functional polyurethane resin, and the mass ratio of the 6-functional polyurethane resin to the 2-functional polyurethane resin is 3-4: 1.
3. The dual cure high gloss black automotive interior coating of claim 2, wherein: the 6-functional polyurethane resin is 6-functional aliphatic polyurethane acrylate, and the 2-functional polyurethane resin is one or two of 2-functional macromolecular aliphatic polyurethane acrylate and 2-functional polycarbonate polyurethane.
4. The dual cure high gloss black automotive interior coating of claim 2, wherein: the 2-functional polyurethane resin is a 2-functional polycarbonate polyurethane.
5. The dual cure high gloss black automotive interior coating of claim 1, wherein: the mass ratio of the polyurethane resin to the dual-curing UV resin is 1: 2-4.
6. The dual cure high gloss black automotive interior coating of claim 1, wherein: the dual-curing UV resin is one or more of L-8464, L-8468 and UA-7706H;
the active monomer is one or more of hydroxyethyl methacrylate, tetrahydrofuran acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, hydroxymethyl propane triacrylate and pentaerythritol triacrylate.
7. The dual cure high gloss black automotive interior coating of claim 1, wherein: the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, a-dimethoxy acetophenone, 2, 4, 6-trimethyl benzoyl-diphenyl phosphine oxide and isopropyl thioxanthone;
the auxiliary agent is one or more of pure acrylate, polyester modified organic siloxane and polyether modified organic siloxane;
the solvent is one or more of ethyl acetate, isobutyl isobutyrate, isopropanol, isobutanol, butyl acetate, propylene glycol methyl ether acetate and propylene glycol methyl ether.
8. The dual cure high gloss black automotive interior coating of claim 1, wherein: the preparation method of the nano black paste comprises the following steps:
(1) adding 57 mass percent of PMA and 23 mass percent of EFKA4310 into a stirring cylinder, stirring until the PMA and the EFKA are completely dissolved, and then adding 20 mass percent of RAVEN 5000UII into the stirring cylinder;
(2) stirring at a high speed of 800r/min for 30min, standing for 24h, and soaking for moistening;
(3) stirring for 30min at 500r/min, pumping into a horizontal sand mill for grinding after uniform stirring until the fineness is below 5 μm, and obtaining the nano black paste.
9. The dual cure high gloss black automotive interior coating of claim 8, wherein: the grinding conditions in the step (3) are as follows: the grinding pressure was 0.2Pa and the grinding temperature was 60 ℃.
10. A method for preparing the dual-curing highlight black automotive interior coating according to any one of claims 1 to 9, characterized in that: the method comprises the following steps: under the environment of completely isolating ultraviolet light by using a yellow light lamp, uniformly stirring 10% of solvent and nano black slurry, sequentially adding an active monomer, a photoinitiator and the rest solvent, uniformly stirring at the speed of 200r/min, sequentially adding dual-curing UV resin, polyurethane resin and an auxiliary agent, and stirring at the speed of 800r/min for 20min to prepare the dual-curing highlight black automobile coating.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN114752268A (en) * 2022-04-01 2022-07-15 惠州市百时达化工有限公司 Double-curing-surface paint for automobile exterior decoration and preparation method and application thereof
CN116589916A (en) * 2023-06-12 2023-08-15 千浪化研新材料(上海)有限公司 Water-based dual-curing weather-resistant environment-friendly efficient interior paint and preparation method thereof

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CN106675365A (en) * 2016-12-21 2017-05-17 东来涂料技术(上海)有限公司 Environmental-friendly type UV (Ultraviolet) double-curing glossy black paint and preparation method thereof
CN108929627A (en) * 2018-06-27 2018-12-04 惠州市嘉淇涂料有限公司 A kind of photo-thermal dual curable plastic coating
CN108997925A (en) * 2018-09-18 2018-12-14 芜湖春风新材料有限公司 A kind of coloured dual cure UV coating of automotive upholstery
CN110982419A (en) * 2019-12-25 2020-04-10 清远雅克化工有限公司 Special high-performance dual-curing UV (ultraviolet) coating for automotive upholstery and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN104098999A (en) * 2013-04-03 2014-10-15 湖北航天化学技术研究所 UV-heat dual-curing polyurethane coating, and preparation method and application thereof
CN106675365A (en) * 2016-12-21 2017-05-17 东来涂料技术(上海)有限公司 Environmental-friendly type UV (Ultraviolet) double-curing glossy black paint and preparation method thereof
CN108929627A (en) * 2018-06-27 2018-12-04 惠州市嘉淇涂料有限公司 A kind of photo-thermal dual curable plastic coating
CN108997925A (en) * 2018-09-18 2018-12-14 芜湖春风新材料有限公司 A kind of coloured dual cure UV coating of automotive upholstery
CN110982419A (en) * 2019-12-25 2020-04-10 清远雅克化工有限公司 Special high-performance dual-curing UV (ultraviolet) coating for automotive upholstery and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114752268A (en) * 2022-04-01 2022-07-15 惠州市百时达化工有限公司 Double-curing-surface paint for automobile exterior decoration and preparation method and application thereof
CN114752268B (en) * 2022-04-01 2023-02-03 惠州市百时达化工有限公司 Double-curing-surface paint for automobile exterior decoration and preparation method and application thereof
CN116589916A (en) * 2023-06-12 2023-08-15 千浪化研新材料(上海)有限公司 Water-based dual-curing weather-resistant environment-friendly efficient interior paint and preparation method thereof
CN116589916B (en) * 2023-06-12 2024-04-12 千浪化研新材料(上海)有限公司 Water-based dual-curing weather-resistant environment-friendly efficient interior paint and preparation method thereof

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