CN114752268A - Double-curing-surface paint for automobile exterior decoration and preparation method and application thereof - Google Patents
Double-curing-surface paint for automobile exterior decoration and preparation method and application thereof Download PDFInfo
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- CN114752268A CN114752268A CN202210349331.0A CN202210349331A CN114752268A CN 114752268 A CN114752268 A CN 114752268A CN 202210349331 A CN202210349331 A CN 202210349331A CN 114752268 A CN114752268 A CN 114752268A
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Chemical & Material Sciences (AREA)
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Abstract
The invention relates to C08F283/01, and particularly relates to a double-curing-side paint for automobile exterior decoration and a preparation method and application thereof. The raw materials comprise the following components in parts by weight: 10-15 parts of matrix resin, 0.5-2 parts of hardening agent, 15-30 parts of polyfunctional group monomer, 5-10 parts of modified resin, 0.4-1 part of photoinitiator, 0.2-0.5 part of flatting agent, 1-5 parts of auxiliary agent and 30-50 parts of organic solvent. The double-curing-surface paint for the automobile exterior trim provided by the invention has the advantages of high scratch resistance, good hydrolysis resistance and waterproof effect, excellent weather resistance and the like.
Description
Technical Field
The invention relates to C08F283/01, and particularly relates to a double-curing-side paint for automobile exterior decoration and a preparation method and application thereof.
Background
The automobile finish is the final coating of an automobile in a coating coloring system of an integral automobile body, and particularly has the functions of good color sense, decorative appearance, protectiveness and weather resistance, so that the integral value of an automobile product can be effectively improved.
In recent years, with the improvement of production living standard, the performance requirements of automobile external finish paint are higher and higher. Especially for the abrasion resistance and light aging resistance tests, the coating test is always difficult.
Patent CN201811070519.1 provides a thermoplastic acrylic resin-based blade coating type intermediate coat automobile paint and a preparation method thereof, and the automobile paint prepared by adopting substances such as thermoplastic acrylic resin, powder, wetting dispersant, pigment dispersant and the like has the advantages of high adhesive force, good wear resistance and the like.
Patent CN201511009422.6 provides an environment-friendly nano-metal automobile finish, which hydroxylates nano-metal slurry by organic acid and cross-links with water-based acrylic resin, amino resin and other substances in the system by a silane coupling agent, so that the automobile finish has high hardness, wear resistance and good scratch resistance.
However, the paint prepared by the prior art has insufficient waterproof capability and poor hydrolysis resistance, and is easily damaged due to the influence of the external environment when being used for automobile exterior decorations.
In order to solve the problems, the application provides the dual-curing finish paint, so that the durability, weather resistance, scraping resistance and the like of a product are improved, the performance of the paint can be integrally improved, the UV paint belongs to environment-friendly paint, and the VOC emission can be effectively reduced.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a dual-curing topcoat paint for automobile exterior decoration, which comprises the following raw materials in parts by weight: 10-15 parts of matrix resin, 0.5-2 parts of hardening agent, 15-30 parts of polyfunctional group monomer, 5-10 parts of modified resin, 0.4-1 part of photoinitiator, 0.2-0.5 part of flatting agent, 1-5 parts of auxiliary agent and 30-50 parts of organic solvent.
As a preferred embodiment, the matrix resin has a viscosity of 250-350 mPas at 25 ℃ in a 40 wt% solution.
Preferably, the average molecular weight of the matrix resin is (25-35) × 103。
As a preferable mode, the matrix resin is at least one of acrylic resin, polyurethane resin and epoxy resin.
More preferably, the matrix resin is a water-based acrylic resin.
As a further preferable mode, the aqueous acrylic resin is an aqueous acrylic resin.
As a preferred embodiment, the hardener is a monofunctional acrylate monomer.
In a preferred embodiment, the monofunctional acrylate monomer includes at least one of methyl methacrylate, ethyl methacrylate, lauryl methacrylate, glycidyl methacrylate, and isobornyl methacrylate.
As a more preferred embodiment, the monofunctional acrylate monomer includes isobornyl methacrylate.
As a preferred embodiment, the hardener has a viscosity of 2 to 10cps at 25 ℃.
As a preferable scheme, the content of the polymerization inhibitor in the hardener is 120-180 ppm.
In a preferred embodiment, the multifunctional monomer includes at least one of a trifunctional monomer, a tetrafunctional monomer, and a hexafunctional monomer.
As a more preferred embodiment, the multifunctional monomer includes a trifunctional monomer and a hexafunctional monomer. The mass ratio of the trifunctional monomer to the hexafunctional group monomer is (12-14): (5-7).
As a preferable scheme, the viscosity of the trifunctional monomer at 25 ℃ is 400-550 cps.
As a preferred embodiment, the trifunctional monomer comprises at least one of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate.
As a more preferred embodiment, the trifunctional monomer includes pentaerythritol triacrylate.
As a preferred embodiment, the viscosity of the hexafunctional monomer is 55000-75000cps at 25 ℃.
In a preferred embodiment, the hexafunctional monomer comprises at least one of dipentaerythritol hexaacrylate, aliphatic polyurethane hexaacrylate, and aromatic polyurethane hexaacrylate.
As a more preferred embodiment, the hexafunctional monomer comprises aliphatic urethane hexaacrylate.
As a still further preferable mode, the mass ratio of the pentaerythritol triacrylate to the aliphatic urethane hexaacrylate is 13: 6.
in the application, the mixture of pentaerythritol triacrylate and aliphatic polyurethane hexaacrylate is used as a polyfunctional monomer in the raw material, so that the volatility of the finish paint can be effectively avoided while the mechanical property and the wear resistance of the finish paint are effectively improved. The applicant believes that: when the mass ratio of pentaerythritol triacrylate to aliphatic urethane hexaacrylate in the present application is 13: 6, the two components have synergistic effect, a controllable chain segment with proper length can be effectively formed, the existence of pentaerythritol triacrylate can also effectively reduce the repulsion phenomenon of polyurethane in an acrylic acid system, and the side chain hydroxyl group can further enhance the molecular polarity of the system, and on the other hand, the side chain hydroxyl group can be used as a reaction site and simultaneously can be connected with a multi-resin end.
As a preferable mode, the modified resin is a dual-curing resin.
As a preferred embodiment, the dual-curing resin is at least one of a UV/EB curing resin and a UV/moisture curing resin.
As a more preferable mode, the modified resin is a UV/EB cured resin.
Preferably, the mass ratio of the modified resin to the matrix resin is (6-7): (14-15).
As a more preferable mode, the mass ratio of the modified resin to the matrix resin is 6.5: 14.
in the application, the UV/EB curing resin is adopted, so that the finish paint is effectively subjected to dual-curing modification, and the comprehensive performance of the finish paint can be further improved. The applicant believes that: when the mass ratio of the modified resin to the matrix resin is 6.5: 14, the modified resin has multiple side chains which can form a good complementary effect with the long linear alkane skeleton formed in the application, so that the entanglement property and the crosslinking property of a system are improved, and the adhesion of the finish paint on the surface of a specific automobile can be further effectively improved due to the existence of the multiple side chains, and the comprehensive performance of the finish paint is improved.
As a preferred embodiment, the photoinitiator comprises at least one of 4-chlorobenzophenone, 4-methylbenzophenone, 3-methyl-4-phenylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, diphenylethanone, 2-hydroxy-2-methyl-1-phenyl acetone.
As a more preferred embodiment, the photoinitiator comprises 2-hydroxy-2-methyl-1-phenylpropanone and 4-methylbenzophenone. The mass ratio of the hydroxy-2-methyl-1-phenyl acetone to the 4-methyl benzophenone is (1-2): (1-2).
As a preferred embodiment, the leveling agent is a polyether polysiloxane copolymer.
As a preferred embodiment, the leveling agent includes a first leveling agent and a second leveling agent. The mass ratio of the first leveling agent to the second leveling agent is (1-2): (1-2).
As a preferable mode, the viscosity of the first leveling agent at 25 ℃ is 2000mPa · s.
As a preferable mode, the viscosity of the second leveling agent at 25 ℃ is 250mPa · s.
In a preferred embodiment, the organic solvent includes at least one of aromatic hydrocarbons, short-chain organic alcohols, ethers, ketones, and esters.
As a more preferable mode, the organic solvent includes an ester compound.
As a preferred embodiment, the ester compound includes ethyl acetate and/or butyl acetate.
In a preferred embodiment, the auxiliary agent comprises a phenolic compound and an amine compound. The mass ratio of the phenolic compound to the amine compound is (1-2): (3-5).
As a more preferred embodiment, the auxiliaries include di-tert-butyl-p-cresol and diphenylamine.
As a still further preferable mode, the mass ratio of di-tert-butyl-p-cresol and diphenylamine is 1.5: 4.
however, the applicant also found that in the present application, the addition of the modified resin and the multifunctional monomer easily initiates electron-losing reactions inside the system in spite of the increased linear chain length and the increased number of side chains, thereby accelerating discoloration and aging of the system. When the auxiliary agent is di-tert-butyl-p-cresol and diphenylamine, the mass ratio of the di-tert-butyl-p-cresol to the diphenylamine is 1.5: 4, the phenols and the amines which are used as the free radical scavenger can capture active free electrons to enable the active free electrons to become inactive electrons and inhibit continuous electron losing reaction, the phenols are beneficial to the regeneration of the amines and can inhibit the atom electron losing reaction for a long time, and the electron losing activity of the compound thickening agent is inhibited by the synergistic effect of the phenols and the amines, so that the flow of electrons in the system and the flow of radicals are further reduced, and the overall stability of the system is improved.
The second aspect of the invention provides a preparation method of a double-curing-side paint for automobile exterior decoration, which comprises the following steps: uniformly mixing matrix resin, a hardening agent, a polyfunctional monomer, modified resin and an organic solvent, heating to 80-85 ℃, preserving heat for 5-10min, then adding a photoinitiator, preserving heat for 1.5-2.5h, cooling, then adding a leveling agent and an auxiliary agent, and uniformly mixing to obtain the high-performance organic silicon/inorganic composite material.
Preferably, the photoinitiator is added in two times, wherein the adding amount of the first photoinitiator is 20-30 wt%, and the adding amount of the first photoinitiator is 70-80 wt%.
The third aspect of the invention provides application of the double-curing-side paint for automobile exterior decoration, which is characterized in that the double-curing-side paint for automobile exterior decoration is applied to the field of automobile exterior decoration.
Has the advantages that:
the paint prepared by the prior art has insufficient waterproof capability and poor hydrolysis resistance, and is easily damaged due to the influence of the external environment when being used for automobile exterior decorations. According to the invention, by adopting the multifunctional monomer of the mixture of pentaerythritol triacrylate and aliphatic polyurethane hexaacrylate and the UV/EB (ultraviolet/Electron beam) curing resin, the binding force among the raw materials is improved, the entanglement and crosslinking among molecular chains are promoted, so that the finish paint has higher adhesive force on the surface of an automobile, the influence of water, chemical solvents and the like on the finish paint is reduced while the mechanical property and the wear resistance of the finish paint are improved, the volatilization of the finish paint is avoided, and the requirements of the state on environmental protection are met. In addition, the invention also adopts di-tert-butyl-p-cresol and diphenylamine to inhibit atom electron losing reaction, so as to avoid poor color retention and poor weather resistance of the finish paint due to excessive active groups, thereby improving the overall performance of the finish paint.
Detailed Description
Examples
Example 1
The double-curing-surface paint for the automobile exterior decoration comprises the following raw materials in parts by weight: 14 parts of matrix resin, 1 part of hardener, 20 parts of polyfunctional group monomer, 6.5 parts of modified resin, 0.7 part of photoinitiator, 0.3 part of flatting agent, 3 parts of auxiliary agent and 40 parts of organic solvent.
The matrix resin is water-based acrylic resin, the viscosity of 40 wt% solution at 25 ℃ is 250-340mPa & s, and the average molecular weight is 30 x 103Purchased from Jingyi New materials Co., Ltd, Guangzhou, type: mitsubishi BR-113.
The hardener is isobornyl methacrylate, the viscosity at 25 ℃ is 2-10cps, the content of the polymerization inhibitor is 120-180ppm, and the model is as follows: chang EM90, purchased from taiwan chang chemical.
The multifunctional monomer comprises pentaerythritol triacrylate and aliphatic polyurethane hexaacrylate. The mass ratio of the pentaerythritol triacrylate to the aliphatic polyurethane hexaacrylate is 13: 6. the viscosity of the pentaerythritol triacrylate at 25 ℃ is 400-550cps, the content of the polymerization inhibitor is 400-600ppm, and the type is as follows: changxing EM 90; the aliphatic polyurethane hexaacrylate has a viscosity of 55000-75000cps at 25 ℃, model number: yangxing 6145-100; the multifunctional monomers were all purchased from taiwan changxing chemistry.
The modified resin is UV/EB (ultraviolet/Electron Beam) cured resin, and the type is as follows: the product can be obtained from Haiyi corporation, Inc. by taking EB8210 as a exquisite material.
The photoinitiator comprises 2-hydroxy-2-methyl-1-phenyl acetone and 4-methyl benzophenone. The mass ratio of the hydroxyl-2-methyl-1-phenyl acetone to the 4-methylbenzophenone is 1: 1. the 2-hydroxy-2-methyl-1-phenyl acetone is purchased from Keye chemical industry, and the model is as follows: basf 1173, germany. The 4-methylbenzophenone is purchased from northHu Dongcao chemical science and technology Co., Ltd, model number: MBZ.
The leveling agent is polyether polysiloxane copolymer and comprises a first leveling agent and a second leveling agent. The mass ratio of the first leveling agent to the second leveling agent is 1: 1. the first leveling agent has a viscosity of 2000mPa & s at 25 ℃, and the type is as follows: digao 410. The second leveling agent has a viscosity of 250mPa · s at 25 ℃, type: digao 450; the leveling agent is purchased from Sanliter trade company of Shuidedistrict of Foshan city.
The organic solvent includes ethyl acetate and butyl acetate. The mass ratio of the ethyl acetate to the butyl acetate is 1: 2.
the auxiliary agent comprises di-tert-butyl-p-cresol and diphenylamine. The mass ratio of the di-tert-butyl-p-cresol to the diphenylamine is 1.5: 4.
a preparation method of a double-curing-side paint for automobile exterior decoration comprises the following steps: uniformly mixing matrix resin, a hardening agent, a polyfunctional monomer, modified resin and an organic solvent, heating to 82 ℃, preserving heat for 8min, then adding 25 wt% of a photoinitiator, preserving heat for 40min, then adding the rest photoinitiator, preserving heat for 1.2h, cooling, then adding a leveling agent and an auxiliary agent, and uniformly mixing to obtain the composite material.
Example 2
The specific implementation manner of the double-curing topcoat paint for automobile exterior trimming is the same as that of example 1, except that the mass ratio of the hydroxy-2-methyl-1-phenyl acetone to the 4-methyl benzophenone is 2: 5.
example 3
The specific embodiment of the double-curing-side paint for the automotive exterior trim is the same as that in example 1, except that the raw materials comprise 15 parts of matrix resin, 1 part of a hardening agent, 25 parts of a multifunctional monomer, 7 parts of modified resin, 0.8 part of a photoinitiator, 0.3 part of a leveling agent, 3 parts of an auxiliary agent and 40 parts of an organic solvent.
Comparative example 1
The specific implementation mode of the double-curing-side paint for the automotive exterior trim is the same as that of example 1, except that the raw materials comprise 14 parts of matrix resin, 1 part of hardener, 20 parts of polyfunctional monomer, 4 parts of modified resin, 0.7 part of photoinitiator, 0.3 part of leveling agent, 3 parts of auxiliary agent and 40 parts of organic solvent.
Comparative example 2
The specific implementation mode of the double-curing-side paint for the automotive exterior trim is the same as that of example 1, except that the mass ratio of the trifunctional monomer to the hexafunctional monomer is 8: 6.
performance test
The dual cure topcoat materials prepared in the examples and comparative examples were tested according to the popular automotive standard TL-226 and the AEPMT.1.6.2.002-2020 test standard.
1. Heat resistance: the heat aging time is 500 h; the aging temperature is 105 +/-2 ℃.
2. Hydrolysis resistance: (90 + -2) ° C, (95 + -3)% RH/72 h. (the product is placed in a temperature cabinet in a suitable position to prevent droplets from forming from dripping on the product), and the test is followed by a cross-hatch (or cross-hatch) and scratch resistance test.
3. Chemical and abrasion resistance and spot test: carrying out 2000 rubfastness tests with dry cloth (suitable for components in heavy-duty areas, such as steering wheels, gear lever handles);
1. carrying out 100 times of rubbing and fading resistance tests on dry cloth;
2. the rub-resistant fading test was performed 100 times with wet cloth (distilled water);
3. with 5% of a surfactant (
Liquid detergent) was subjected to 10 rubfastness test;
4. alcohol cleaning solution containing amino group (A)
Glass cleaner) was subjected to 10 rubfastness tests;
5. carrying out 10 times of friction-resistant fading tests by using petroleum ether (according to the boiling point range of 80-100 ℃);
6. modified alcohol [ ethanol 99%, butanone 1%, analytical purity ] was subjected to rubbing-resistant fading test for 10 times;
7. synthetic sweat A [ 0.75% acetic acid (7.5 mL 100% acetic acid and distilled water to constant volume of 1L) ] was subjected to 10 rubfastness test
8. Synthetic sweat B [ aqueous ammonia solution (1g NH3 solution +3.47g NaCl +690mL water) ] was subjected to 10 rubout resistance tests and passed.
4. Xenon lamp aging test: PV 1303-2015.
Table 1 results of performance testing
Claims (10)
1. The double-curing-surface paint for the automobile exterior decoration is characterized by comprising the following raw materials in parts by weight: 10-15 parts of matrix resin, 0.5-2 parts of hardening agent, 15-30 parts of polyfunctional group monomer, 5-10 parts of modified resin, 0.4-1 part of photoinitiator, 0.2-0.5 part of flatting agent, 1-5 parts of auxiliary agent and 30-50 parts of organic solvent.
2. The dual-cure topcoat paint for automobile exterior applications as claimed in claim 1, wherein the viscosity of a 40 wt% aqueous solution of the matrix resin at 25 ℃ is 250-350 mPa-s.
3. The dual cure topcoat paint for automobile exterior trimming as claimed in claim 2, wherein the matrix resin comprises at least one of acrylic resin, urethane resin, epoxy resin.
4. The dual cure topcoat paint for automotive exterior, according to claim 1, wherein the hardener is a monofunctional acrylate monomer.
5. The dual-cure topcoat paint for automobile exterior trimming as claimed in claim 1, wherein the multifunctional monomer comprises at least one of a trifunctional monomer, a tetrafunctional monomer and a hexafunctional monomer.
6. The dual-curing topcoat paint as claimed in claim 5, wherein the trifunctional monomer comprises at least one of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate.
7. The dual cure topcoat paint for automobile exterior trimming as claimed in claim 5, wherein the hexafunctional monomer comprises at least one of dipentaerythritol hexaacrylate, aliphatic polyurethane hexaacrylate, and aromatic polyurethane hexaacrylate.
8. The dual cure topcoat paint for automobile exterior trim according to claim 1, wherein the modified resin is a dual cure resin.
9. A method for preparing the double curing surface paint for automobile exterior finishing according to any one of claims 1 to 8, characterized by comprising the steps of: uniformly mixing matrix resin, a hardening agent, a polyfunctional monomer, modified resin and an organic solvent, heating to 80-85 ℃, preserving heat for 5-10min, then adding a photoinitiator, preserving heat for 1.5-2.5h, cooling, then adding a leveling agent and an auxiliary agent, and uniformly mixing to obtain the high-performance organic silicon/inorganic composite material.
10. Use of the double-curing-side paint for automobile exterior finishing according to any one of claims 1 to 8, wherein the double-curing-side paint for automobile exterior finishing is applied to the field of automobile exterior finishing.
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| CN202210349331.0A CN114752268B (en) | 2022-04-01 | 2022-04-01 | Double-curing-surface paint for automobile exterior decoration and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926598A (en) * | 2022-12-31 | 2023-04-07 | 惠州市韵点新材料科技股份有限公司 | Dual-curing UV (ultraviolet) finish paint and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796478A (en) * | 2004-12-20 | 2006-07-05 | 比亚迪股份有限公司 | Coating material solidified by ultraviolet light and prepartion method |
| CN113817402A (en) * | 2021-07-27 | 2021-12-21 | 广东希贵光固化材料有限公司 | Dual-curing highlight black automobile interior coating and preparation method thereof |
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2022
- 2022-04-01 CN CN202210349331.0A patent/CN114752268B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796478A (en) * | 2004-12-20 | 2006-07-05 | 比亚迪股份有限公司 | Coating material solidified by ultraviolet light and prepartion method |
| CN113817402A (en) * | 2021-07-27 | 2021-12-21 | 广东希贵光固化材料有限公司 | Dual-curing highlight black automobile interior coating and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926598A (en) * | 2022-12-31 | 2023-04-07 | 惠州市韵点新材料科技股份有限公司 | Dual-curing UV (ultraviolet) finish paint and application thereof |
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